Use of Bromine and Bromo-Organic Compounds in Organic Synthesis

Review pubs.acs.org/CR

Use of Bromine and Bromo-Organic Compounds in Organic Synthesis Indranirekha Saikia, Arun Jyoti Borah, and Prodeep Phukan* Department of Chemistry, Gauahti University, Guwahati-781014, Assam, India ABSTRACT: Bromination is one of the most important transformations in organic synthesis and can be carried out using bromine and many other bromo compounds. Use of molecular bromine in organic synthesis is well-known. However, due to the hazardous nature of bromine, enormous growth has been witnessed in the past several decades for the development of solid bromine carriers. This review outlines the use of bromine and different bromo-organic compounds in organic synthesis. The applications of bromine, a total of 107 bromo-organic compounds, 11 other brominating agents, and a few natural bromine sources were incorporated. The scope of these reagents for various organic transformations such as bromination, cohalogenation, oxidation, cyclization, ringopening reactions, substitution, rearrangement, hydrolysis, catalysis, etc. has been described briefly to highlight important aspects of the bromo-organic compounds in organic synthesis.

CONTENTS 1. Introduction 2. Scope of This Review 3. Bromination Reactions 3.1. Bromination with Molecular Bromine 3.1.1. Bromination of Olefinic Compounds Using Molecular Bromine 3.1.2. Bromination of the Aliphatic C−H Bond Using Molecular Bromine 3.1.3. Aromatic Ring Bromination Using Molecular Bromine 3.1.4. Bromination of Heterocyclic Compounds with Molecular Bromine 3.1.5. Bromination of Naturally Occurring Compounds Using Molecular Bromine 3.1.6. Miscellaneous Bromination Reactions Using Molecular Bromine 3.2. Bromination with Bromo-Organic Compounds 3.2.1. Bromination with NBS 3.2.2. Bromination with Other Bromo-Organic Compounds 3.3. Reagents Other Than Bromo-Organic as Well as Naturally Occurring Bromo Compounds 3.3.1. HOBr 3.3.2. Phosphorus Oxybromide 3.3.3. Triphasic System of Bu4N+HSO4−, NaBr, and NaOCl 3.3.4. Ammonium Bromide 3.3.5. Iodine Monobromide 3.3.6. Boron Tribromide 3.3.7. Bromine Chloride 3.3.8. Thionyl Bromide © 2016 American Chemical Society

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3.3.9. Bromine Fluoride 3.3.10. Bromine Triflouride 3.3.11. HBr 3.3.12. Bromoiodinanes 3.3.13. Alkyl Hypobromites 3.3.14. Natural Sources Cohalogenation Reactions 4.1. Cohalogenation Reactions Using Molecular Bromine 4.2. Cohalogenation Reaction with NBS 4.3. Cohalogenation Reaction with Other Bromo-Organic Compounds Oxidation Reactions 5.1. Use of Molecular Bromine as an Oxidant 5.2. Application of NBS to Oxidation Reactions 5.3. Oxidation Reactions Using Other BromoOrganic Compounds Cyclization Reactions 6.1. Use of Molecular Bromine for Cyclization Reactions 6.2. Use of NBS in Cyclization Reactions 6.3. Cyclization Reactions Using Other Bromo Compounds Formation of Nitro Compounds 7.1. Formation of Nitro Compounds Using Bromonitromethane 7.2. Use of Other Bromo-Organic Compounds for the Formation of Nitro Compounds Rearrangement Reactions 8.1. Molecular Bromine-Assisted Rearrangement Reactions 8.2. Rearrangement Reactions Using NBS

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Received: September 1, 2015 Published: May 20, 2016 6837

DOI: 10.1021/acs.chemrev.5b00400 Chem. Rev. 2016, 116, 6837−7042

Chemical Reviews 8.3. Rearrangement Reactions in the Presence of Other Bromo-Organic Compounds 9. Hydrolysis Reactions 10. Aziridination Reactions 11. Ring-Opening Reactions 12. Substitution Reactions 12.1. Substitution Reactions Using Molecular Bromine 12.2. NBS-Mediated Substitution Reactions 12.3. Substitution Reactions with Other BromoOrganic Compounds 13. Protection and Deprotection Reactions 14. Miscellaneous Reactions 14.1. Miscellaneous Reactions Using Molecular Bromine 14.2. Miscellaneous Reactions Using NBS 14.3. Miscellaneous Reactions Using Other Bromo-Organic Compounds 15. Catalysis 15.1. Use of Molecular Bromine as a Catalyst 15.2. Catalytic Applications of NBS 15.3. Catalytic Use of Bromodimethylsulfonium Bromide (BDMS) 15.4. Use of Other Bromo-Organic Compounds as Catalysts 16. Conclusion Author Information Corresponding Author Notes Biographies Acknowledgments References

Review

available in the literature and their uses for organic transformations.

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2. SCOPE OF THIS REVIEW In the past several decades, numerous brominating agents were introduced for bromination and other synthetic transformations. In light of the rapidly growing literature on this subject, a unified discussion has been made to highlight the use of bromine and bromo-organic compounds in organic synthesis. The review covers the literature to date. The selection of bromo-organic compounds in this work is based primarily on their potential for bromination reactions. This work summarizes the applications of the following bromo-organic compounds in organic synthetic transformations: (1) Nbromosuccinimide, (2) ammonium bromide, (3) N-bromoacetamide, (4) bis(dimethylacetamide) hydrogen dibromobromate, (5) benzalkonium tribromide (6) 1-benzyl-4-aza-1azoniabicyclo[2.2.2]octane tribromide, (7) benzimidazolium bromochromate, (8) benzyltriethylammonium tribromide, (9) benzyltrimethylammonium tribromide, (10) benzyltriphenylphosphonium tribromide, (11) bromamine-T, (12) Nbromobenzamide (benzbromamide), (13) N-bromo-tert-butylamine, (14) 2-bromo-2-cyano-N,N-dimethylacetamide, (15) bromodichloroisocyanuric acid, (16) 1-bromo-5,5-diethylbarbituric acid and 1,3-dibromo-5,5-diethylbarbituric acid, (17) bromodimethylsulfonium bromide, (18) 3-bromo-4,4-dimethyl-2-oxazolidinone, (19) 3-bromo-5,5-dimethylhydantoin, (20) 3-bromo-3-(ethoxycarbonyl)-2,4-dioxo-1,2,3,4-tetrahydroquinones, (21) bromonitromethane, (22) N-bromophthalimide, (23) N-bromosaccharin, (24) (tert-butylamino)triphenylphosphonium tribromide, (25) tert-butyl N,N-dibromocarbamate, (26) 1-butyl-3-methylimidazolium tribromide, (27) 1-butyl-3methylpyridinium tribromide, (28) bromine supported on resin, (29) carbon tetrabromide, (30) cetylpyridinium tribromide, (31) cetyltrimethylammonium tribromide, (32) chiral brominating agent, (33) cross-linked poly(vinylpyridinium hydrobromide perbromide) resins, (34) crown ether complex of molecular bromine, (35) cyanogen bromide, (36) 2,4-diamino-1,3-thiazole hydrotribromide, (37) 1,8-diazabicyclo[5.4.0]undecene-7-bromotrichloromethane, (38) 1,8-diazobicyclo[5.4.0]undec-7-ene hydrobromide perbromide, (39) N,N-dibromobenzenesulfonamide, (40) N,N′-dibromo-N,N′(1,2-ethylene)bis(4-methylbenzenesulfonamide), (41) N,N′dibromo-N,N′-(1,2-ethylene)bis(2,5-dimethylbenzenesulfonamide), (42) 2,2-dibromo-2-cyano-N,N-dimethylacetamide, (43) 1,2-dibromoethane, (44) 5,5-dibromo-2,2-dimethyl-4,6dioxo-1,3-dioxane, (45) 1,3-dibromo-5,5-dimethylhydantoin, (46) 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione, (47) 4,4-dibromo-3-methylpyrazol-5-one, (48) N,N-dibromo-p-toluenesulfonamide, (49) diethyl N,N-dibromophosphoroamidate, (50) 1,1′-(1,2-ethanediyl)dipyridinium bistribromide, (51) dibromoisocyanuric acid, (52) N,N-dibromomethanamine and N-bromomethanamine, (53) 4-(dimethylamino)pyridinium bromide perbromide, (54) dioxane dibromide, (55) ethylenebis(N-methylimidazolium) bistribromide, (56) ethyl tribromoacetate, (57) hexabromoacetone, (58) imidazo[1,2-b] pyridazine−bromine [(a) 3-bromo-6-chloro-2-methylimidazo[1,2-b]pyridazine−bromine, (b) 3-bromoimidazo[1,2-b]pyridazine−bromine, (c) 3-bromo-6-chloroimidazo[1,2-b]pyridazine−bromine], (59) [ [K·18-crown-6]Br3]n, (60) N-methylpyrrolidin-2-one hydrotribromide, (61) 2-methyl-4poly(styrylmethyl)thiazolium hydrotribromide, (62) N-octylquinolinium tribromide, (63) pentylpyridinium tribromide,

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1. INTRODUCTION Bromine is one of the most important and essential members in the periodic table. A wide range of bromo-organic compounds found in nature are formed through photochemical reactions,1geothermal events,2 and metabolic pathways.3,4The bromo-organics are mainly used as flame-retardants, biocides, gasoline additives, halons, polymers, pharmaceuticals, agrochemicals, and dyes.5−11They also play an important role as intermediates in the production of agrochemicals and pharmaceuticals. Elemental bromine is used to manufacture a wide variety of bromo compounds used in industry and agriculture. However, there is risk in handling bromine, as elemental bromine is hazardous and is a strong irritant. It produces painful blisters on exposed skin and especially mucous membranes. Even a low concentration of bromine vapor can affect breathing, and significant amounts of bromine can damage the respiratory system.12Therefore, the use and handling of bromine needs special precautions. Sometimes, this reagent is not selective. In some cases, an extra catalyst has to be added to promote bromination using bromine. Therefore, different brominating reagents have been developed to make bromination procedures more effective and selective. A legion of brominating agents have been developed by a number of researchers across the globe in the passing years. Since we are working in this field to explore new strategies using brominating agents, we have a keen desire to make a compilation of their synthetic uses. Here in this review we made a sincere effort to list the brominating agents already 6838


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(64) perbromides and N-bromo derivatives of ε-caprolactum and of α-aminocaproic acid cyclooligoamides, (65) phenyltrimethylammonium tribromide, (66) pyridinium hydrobromide perbromide, (67) pyridinium perbromide, (68) pyridine sulfate dibromide, (69) pyridinium bromochromate, (70) pyridinium dichlorobromate, (71) pyridine and quinoline derivatives of poly(methyl methacrylate), (72) pyrrolidinone hydrotribromide, (73) poly(N-bromoacrylamine), (74) poly[(vinylbenzyl)triphenylphosphonium perbromide], (75) poly(Nbromosuccinimide), (76) polymeric 1,4-diazabicyclo[2.2.2] octane (DABCO)−bromine, (77) poly(N-bromobenzene-1,3disulfonamide), (78) poly(diallyldimethylammonium tribromide), (79) poly(vinylpyrrolidone)−bromine complex, (80) cross-linked poly(4-vinylpyridine-styrene)−bromine complex, (81) quinolinium bromochromate, (82) quinoxalinium bromochromate, (83) sodium monobromoisocyanurate, (84) silicasupported quinolinium tribromide, (85) tetraalkylammonium bromates, (86) tetraalkylammonium dichlorobromate, (87) tetrabromo hydrogenated cardanol or 2,4,4,6-tetrabromo-3-npentadecyl-2,5- cyclohexadienone, (88) N,N,N′,N′-tetrabromobenzene-1,3-disulfonamide, (89) tetrapropylammonium bromochromate, (90) tetrabutylammonium bromochromate, (91) N,N,N′,N′-tetrabromobenzene-1,3-disulfonamide, (92) tetrameric DABCO−bromine, (93) tetraethylammonium tribromide, (94) tetrabutylammonium tribromide, (95) tetraethylammonium bromide, (96) tetrabutylammonium bromide, (97) tetramethylammonium bromide, (98) tetramethylammonium tribromide, (99) tribromo-m-cresol bromide, (100) tetrabromo-o-benzoquinone, (101) o-polybromoquinone, (102) tribromoisocyanuric acid, (103) 3-(2,2,2-trimethylhydrazinium)propionic acid and its methyl ester and 3-(2,2,2-trimethylhydrazinium)propionate perbromide, (104) tribromoacetic acid, (105) trimethylsilyl bromide, (106) triphasic system of Bu4N+HSO4−, NaBr, and NaOCl, (107) methyltriphenylphosphonium tribromide, (108) tetrapropylammonium nonabromide. Apart from the above bromo-organic compounds, we also discuss herein the use of different nonmetallic as well as naturally occurring bromo compounds in synthetic organic transformations: (109) HOBr, (110) phosphorus oxybromide, (111) iodine monobromide, (112) boron tribromide, (113) bromine chloride, (114) thionyl bromide, (115) bromine fluoride, (116) bromine trifluoride, (117) HBr, (118) bromoiodinanes, (119) alkyl hypobromites, (120) natural sources.

Scheme 1

bromine to 3-ethoxyprop-1-ene at a low temperature in the presence of a solvent.21 α,β-Dibromosuccinic acid was synthesized by the reaction of fumeric acid and Br2 to give a 72−84% yield (Scheme 2).22 Scheme 2

Movsumzade studied the conjugated halogenation of unsaturated compounds. Halogenation of cyclohexene, 3chloro- and 3-bromo-1-propene, and styrene using Cl2 or Br2 in Ac2O yielded 1-acetoxy-2-chloro- and 1-acetoxy-2-bromocyclohexane, 2-acetoxy-1,3-dichloro- and 2-acetoxy-1-bromo-3chloropropane, and 1-acetoxy-1-phenyl-2-chloro- and 1-acetoxy-1-phenyl-2-bromoethane in 76% yield.23 The ring double bond in 4-vinylcyclohexene reacts faster with Br2 than did the vinyl group; the initial product was 3,4-dibromo-1-vinylcyclohexane.24 Exposure of solid α,β-unsaturated acids, amides, and ketones to bromine at room temperature gave the trans adduct in quantitative yield.25 Bromination of cinnamalacetophenone with Br2, suspended in heptane or cyclohexane, gave tetrabromide with a small amount of di- and hexabromides.26 1,1-Diphenyl-2-(2-thienyl)ethylene was brominated by Bottino et al.27 with excess bromine in acetic acid. Naae28 studied the electrophilic bromination of fluoro olefins. The ionic addition of bromine in glacial acetic acid to fluoro olefins has been studied. For all olefins, the 1,2-dibromo adduct is the predominant product, with a minor amount of the 1-acetoxy2-bromo adduct being formed (Scheme 3). Scheme 3

Harwood reported that iodine and Br2 in the presence of sodium benzenesulfinate reacted with aliphatic, cyclic, and aromatic alkenes to give anti-Markovnikov β-halosulfones.29 For example, 27% 1-[(2-bromo-2-phenylethyl)sulfonyl]benzene was obtained on treating styrene with bromine and sodium benzenesulfinate in propanone at ambient temperature and in darkness for 24 h. 1,2-Dibromo-3-chloropropane was prepared by reacting bromine and 3-chloropropene at 60−90 °C.30 The radical bromination reaction of ethylene carbonate was carried out in the presence of benzoyl peroxide by adding Br2 slowly at 130 °C. Both the Br• radical and the Br− ion were involved in the reactions to give several ring-opened esters.31 Bromination of 4-cyclohexene-1,2-dicarboximides by bromine in CHCl3 for 1.5 h at 60−62 °C produced dibromo derivatives and tetrabromo derivatives. 32 Mayr et al. brominated octamethylcyclopentene under mild conditions with Br2 in CCl4 at 20 °C.33 Zabicky et al. carried out the reaction of bromine and cyclohexene in aqueous media and studied the selectivity of bromohydrin vs dibromo adduct formation. Olefin

3. BROMINATION REACTIONS 3.1. Bromination with Molecular Bromine

Elemental bromine is a versatile brominating agent. It can be used for bromination of different types of substrates. Generally, organic compounds are brominated by either addition or substitution reactions. Bromine undergoes electrophilic addition to the double bonds of alkenes. Bromine also undergoes electrophilic substitution to aromatic substrates. 3.1.1. Bromination of Olefinic Compounds Using Molecular Bromine. Elemental bromine can be directly used for bromination of various substrates. Bromine is most widely used for determination of organic unsaturation. This involves the reaction of bromine with the unsaturated compound with a bromonium ion or bromocarbocation as the key intermediate (Scheme 1).13−19 Read described the action of bromine in water on ethylene.20 Ethyl bromofluoropropyl ether was obtained by the addition of 6839


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suspensions in water yield mainly the dibromo adduct when treated with neat liquid Br2, or bromohydrin when treated with aquous Br2.34 Bromination of a combination of chloroprene and ethylene oxide with Br2−CCl4 produced a mixture of bromo compounds (Scheme 4).35

Scheme 6

Regioselective monobromination of 2,4- and 2,6-tolylene diisocyanates was accomplished under dark, radical-free conditions with Br2.36 A method for preparing hexabromocyclododecane comprised the steps of reacting 1,5,9-cyclododecatriene with Br2 in a saturated aliphatic alcohol in the presence of a catalytic amount of a BF3 complex and neutralizing the reaction mixture with a nonaquous base.37 Shi et al. studied the reaction of bromine with cycloalkene via a Friedel−Crafts-like alkylation process.38 Arcus and co-workers carried out the addition reaction of bromine to (+)-1phenylallyl alcohol to give 1-(1,2,3-tribromopropyl)benzene in dry chloroform, carbon tetrachloride, and carbon disulfide (Scheme 5).39 However, the reaction yield was very poor.

The bromine addition to four derivatives of 2-methylocta2,6-dien-4-yne was investigated by Olejnik et al. It has been found that the double bond adjacent to two methyl groups does not participate in the bromine addition. Two types of bromo derivatives have been obtained, dibromotrienes and tribromotrienes.47 The radical reaction of bromine with cyclohexene in carbon tetrachloride in the presence of light was investigated by McMillen et al. Bromine addition to the double bond and allylic substitution occur at comparable rates at room temperature.48 2,3-Dibromo-2-butene-1,4-diol was prepared by bromination of but-2-yne-1,4-diol in an aqueous medium at 10−95 °C.49 Bromination of tetrafluorobenzobarrelene by bromine produced stereoisomers of the annulated tricyclic dibromide, but if pyridine, 15-crown-5, or dimethyl sulfide was present, the transdibromide was obtained as the main or sole product.50 The αoxophosphonium ylide reacted with bromine in the presence of a range of nucleophiles to give monobromo product diethyl-2acetoxy-3-bromofumarate.51 2(S,R),3(R,S)-2,3-Dibromo-3methyl-5-phenylpentanoic acid was prepared by treatment of (E)-3-methyl-5-phenylpent-2-enoic acid with bromine in chloroform (Scheme 7).52

Scheme 5

Scheme 7

Scheme 4

Asymmetric halomethoxylation of chiral α,β-unsaturated carboxylic acid derivatives was performed with bromine promoted by silver(I) salts with high regio- and antiselectivity and moderate to good diastereoselectivity (Scheme 8).53

In the regiospecific and stereospecific synthesis of E- and Ztrisubstituted alkenes via 2,2-disubstituted vinylsilanes, Chou carried out an electrophilic substitution reaction with Br2.40 Treatment of methyl 2,3-pentadienoate with bromine in carbon tetrachloride afforded a complex mixture composed of (E)- and (Z)-methyl-3,4-dibromopent-2-enoate and 4-bromo-5-methyl5H-furan-2-one as the main products.41 Treatment of cisbicyclo[4.3.0]nona-3,7-diene with Br2 at −8 °C produced a 2:1 mixture of tetrabromides with a trans-diaxial and transdiequatorial distribution of bromine in the six-membered ring and only trans bromine atoms in the five-membered ring.42 Fuller et al. used Br2 in the synthesis of isomerically pure cis-1bromopropene. Reaction of trans-crotonic acid with Br2 (1.5 equiv) in heptane produced an 88% yield of erythro- 2,3dibromobutanoic acid. Furthe r treatment of this compound led to the desired product.43 The reaction of alkenes and arylalkenes with Br2 in damp acetonitrile occurred with solvent incorporation to give 2-bromo-1-(acetylamino)alkanes, 2methyloxazolines, (2-acetoxyalkyl)amine hydrobromides, and 2-(acetylamino) alcohols.44 Zelikman et al. studied the bromination of unsaturated compounds by bromine and hydrogen chloride at low temperature. The reaction was carried out with 1-hexene, ethene, 3,4-dichloro-1-butene, trans1,4-dichloro-2-butene, and 3-chloro- and 3-bromopropene; styrene failed to give the reaction.45 Stirring methyl acrylate with THF and Br2 at room temperature gave a 97% yield of methyl 2-bromo-3-(4-bromobutoxy)propionate, which was treated with triethylamine to produce methyl α-bromoacrylate in 92% yield (Scheme 6).46

Scheme 8

Fluorine-containing olefins were brominated with bromine in the dark in the presence of metal powders or Lewis acids to give the dibromo product by Yotsuya et al. Thus, bromination of 3,3,3-trifluoropropene with bromine in the dark in the presence of ferric chloride for 15.3 h produced a 95.2% yield of 1,2-dibromo-3,3,3-trifluoropropane.54 Bromination with molecular bromine can be done through a fluorous multiphase system. Bromine diffuses slowly through the fluorous phase into the organic phase and therefore, without dropwise addition of bromine, stirring, or cooling, reacts moderately and efficiently with the substrate to give the product. Thus, brominations of cyclohexene, 2-octene, p-chloroacetophenone, etc. were described. 55 Conversion of propene to 1,2dibromopropane was done by reaction with Br2 at atmospheric pressure.56 The bromination of unsymmetrical cross-conjugated dienones of cyclohexanes containing terminal thienyl and aryl substituents was carried out by using Br2 in CHCl3 at 0 °C. A mixture of regioisomeric dibromo compound resulted by adding Br2 to the exocyclic double bond. The total yield was 6840


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43−76%, with the different ratios of regioisomers depending on the nature of the substituents in the benzene ring.57 Shellhamer et al. performed photochemical and ionic reactions of Br2 with 4-bromo-1,1,2-trifluorobut-1-ene to give the expected 1,2products in good yield. In methanol as the solvent, both regioisomeric products 1-bromo-2-methoxy and 2-bromo-1methoxy were also formed.58 Shao prepared hexabromocyclododecane by bromination of 1,5,9-cyclododecatriene with Br2 (at a ratio of 1:3.1−3.3) in a mixed solvent.59 Terminal acetylenic compounds were prepared in large scale and in high yield and selectivity by the bromination−dehydrobromination by Br2−NaOH from the corresponding α-olefinic compound.60 2(R,S),3(S,R)-2,3-Dibromo-3-methyl-5-phenylpentanoic acid was prepared by treatment of (Z)-3-methyl-5-phenylpent-2enoic acid with bromine in chloroform.61 The reactivity of the anhydrodihydroartemisinin and of its 10-trifluoromethyl analogue toward brominating reagents was explored by Grellepois et al. with the aim of preparing the new corresponding C-16 allylic bromides. The allylic bromination occurred in high yield with bromine in carbon tetrachloride at 0 °C (Scheme 9).62

Scheme 10

2-, and 3-hexyne on treatment with bromine produce addition (Br2 and HBr) and substitution products.69 Bromination of ethyne with bromine produced cis- and trans-1,2-dibromoethene and 1,1,2,2-tetrabromoethane, which were separated by gas chromatography.70 The bromination of cinnamalacetophenone with bromine proceeded smoothly and gave a yield of 92% of 2,3,4,5-tetrabromo-1,5-diphenylpentan-1-one.71 Bromination of a series of isoprenoid polyenynes by bromine under heterolytic conditions proceeds regioselectively by addition only to the triple bond. Thus, bromination of a mixture of isoprenoids by bromine in butoxytoluene and chloroform at −10 °C produced a 95% yield of the adduct as a mixture of stereoisomers.72 Acetylenes were stereoselectively brominated by bromine adsorbed on graphite in CH2Cl2 to produce (E)α,β-dibromoalkenes. Isomerization of the E-isomer to the Zisomer, usually catalyzed by Br2, did not occur in the presence of graphite.73 Al-Hassan performed bromination of alkynes and alkynylsilanes with molecular bromine to give 1,2-dibromoalkenes and 1,2-dibromovinylsilanes. First, he investigated the bromination of diphenylacetylene and obtained a 95% yield of the corresponding dibromide. The use of 2 equiv of Br2 did not produce the tetrabromo product under the same reaction condition (−12 °C). Again, various alkynylsilanes were treated with 1.2 equiv of bromine in carbon tetrachloride at −12 °C for 0.5 h to produce a good yield of the dibromide (Scheme 11).74

Scheme 9

A highly regio- and stereoselective halohydroxylation of 1,2allenyl sulfoxides and water to give (E)-halovinyl sulfoxides was developed. In the bromohydroxylation, bromine was used as one of the brominating agents. When using bromine, the addition of LiOAc·2H2O was necessary for high yields of the halohydroxylation products.63 One-carbon homologated N-(αhaloacyl)benzotriazoles have been synthesized from the corresponding aromatic and aliphatic aldehydes by Katritzky et al. Here, in one intermediate step, vinylbenzotriazoles were treated with Br2/Et3N to give 1-(bromovinyl)benzotriazoles.64 5-Chloro-3-methyl-1-phenylpyrazole-4-carboxaldehyde reacted with 3-acetyl-4-hydroxy-6-methyl-2-pyranone and 3-acetyl-4hydroxy-2-benzopyranone via Claisen−Schmidt condensation to afford the respective heterochalcones, which underwent facile cyclization with hydrazines to give the corresponding 3,5diheteroaryl-2-pyrazolines. Furthermore, the heterochalcones underwent bromomethoxylation using Br2/MeOH in the presence of lead nitrate or silver nitrate to afford the respective addition products, 3-methoxy-2-bromopropanoyl derivatives.65 1-Ethynylbenzene was stereoselectively brominated by bromine adsorbed on graphite in CCl4 to produce 1-((E)-1,2dibromovinyl)benzene. In this case, the solid support graphite has an important role which inhibits the isomerization of the Eisomer to the Z-isomer, which is usually catalyzed by Br2.66 An experiment was described by Strom et al. in which (E)-βbromostyrene was synthesized by addition of bromine to (Z)-βbromostyrene to form 1-phenyl-1,2,2-tribromoethane, which is debrominated to form (E)-β-bromostyrene (Scheme 10).67 Ethylene bromide was prepared from acetylene by passing the reactant and Br2 over pumice in a reaction tube heated to 160−170 °C.68 About 60% of the ethylene gas was combined to produce the corresponding brominated product. Similarly, 1-,

Scheme 11

Bromination of ethyl propiolate with bromine in carbon tetrachloride produced 93% (Z)-ethyl 2,3-dibromoacrylate, which on Pd(PPh3)4/CuI-catalyzed coupling reaction with (trimethylsilyl)acetylene in the presence of Hunig’s base in dimethylformamide (DMF) produced (Z)-ethyl 2-bromo-5(trimethylsilyl)pent-2-en-4-ynoate in 56% yield (Scheme 12).75 Scheme 12

Bromination of 1-(phenylselenyl)-1-alkynes was studied by Al-Hassan using Br2 in CCl4 to produce the corresponding dibromoalkenes in 80% yield (Scheme 13).76 For example, phenyl(2-phenylethynyl)selane reacts with Br2−CCl4 to produce an 80% yield of ((E)-1,2-dibromo-2-phenylvinyl) phenylselane. Reactions of element-substituted alkynes were studied with bromine by Selina et al. The isomeric Z/E ratios of dibromoalkenes formed in bromination with bromine were also discussed.77 Bromination of a 1,4-butynediol aqueous solution with bromine was carried out at 8−13 °C for 1−1.2 h 6841


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Scheme 13

Scheme 16

followed by reaction for 25−35 min to give 2,3-dibromo-2butene-1,4-diol.78 Reaction of phenylacetylene with SnCl4−Br2 in CCl4 produced mostly (E)-α-chloro-β-bromostyrene, which could be thermally isomerized to the Z-isomer. (E/Z)-α,βDibromobromostyrene, 1-(1,2-dibromo-1,2-dichloroethyl)benzene, and 1-(2-bromo-1,1-dichloroethyl)benzene were also obtained as byproducts.79 Thermostable γ-1,2,5,6,9,10-hexabromocyclododecane was prepared by bromination of 1,5,9cis,trans,trans-cyclododecatriene with Br2 in the presence of a solvent system (Scheme 14).80 Hexabromocyclododecane was prepared in 90−98% yield by bromination of cyclododecatriene with bromine in propanol containing 2−5% H2O.81

A side chain benzoxazine functional polybutadiene (PBbenzoxazine) was synthesized by using a click chemestry strategy.85 First, some of the double bonds were brominated with bromine in carbon tetrachloride and subsequently converted to azido groups by using NaN 3 in DMF. Propargylbenzoxazine was prepared independently by a ringclosure reaction between (propargyloxy)aniline, paraformaldehyde, and phenol. Finally, azido-functionalized polybutadiene was coupled to propargylbenzoxazine with high efficiency by click chemistry. Bromination and subsequent ethylenediamine substitution of the CC double bond in mesoporous ethylenesilica were carried out by Nakai et al.86 The ethylenediamine (EDA)-functionalized mesoporous ethylenesilica (PMO) was prepared by bromine addition and subsequent substitution by EDA. Bromine was added to 45% of the CC double bonds in PMO. Brominations were done using bromine at room temperature. Arsenate adsorption was carried out on the structures that were formed. Treatment of cis- or trans-4-phenylbut-3-en-2-one with bromine gave only the erythro- and threo- 3,4-dibromo-4-phenylbutan-2-one in trifluoroacetic acid or acetic acid (Scheme 17), whereas, in methanol, only the bromomethoxy compounds were observed.87

Scheme 14

Dimethyl 3,6-endoxodihydrophthalate, when treated with aqueous bromine in the presence of potassium bromide, produced the corresponding dibromide, which was subsequently converted to pyrazoline and triazoline derivatives. Bromination, however, in carbon tetrachloride or chloroform produced the cis-dibromide. The trans isomer formed with methanol in the presence of oleum from the trans-dibromo acid.82 Zhou et al. studied the electrophilic reaction of bromine with 1,2-allenyl sulfones.83 The reaction of 1,2-allenyl sulfones with bromine produced E-bromohydroxylation− or E-bromination−elimination products (Scheme 15). The reaction was highly regio- and stereoselective depending on the substitution pattern of the allene functionality.

Scheme 17

Scheme 15 Wyrzykiewicz et al. prepared α,α′-dibromo-2′,4′-dinitro-2(or 3 or 4)-(acetyloxy)bibenzyls by treating stilbenes with bromine. Thus, treating (E)-2′,4′-dinitro-4-acetoxystilbene with bromine in carbon tetrachloride afforded a 72% yield of the product.88 Haynes and co-workers investigated the reaction of (Z)-1,2diphenylethene (cis-stilbene) with bromine as well other brominating reagents.89 Bromine in glacial acetic acid gave a 66% yield of the d,l-product and a 20% yield of the meso product from (Z)-1,2-diphenylethene. However, bromine in dichloromethane gave about equal amounts of the two dibromo products. Similarly, other combinations of reagents were also tested. Bellucci et al. also investigated preassociation, free-ion, and ion-pair pathways in the electrophilic bromination of substituted cis- and trans-stilbenes in protic solvents.90 3-(2,4Dialkoxyphenyl)-5-(substituted phenyl)isoxazoles were prepared by slow addition of a solution of bromine in chloroform to a solution of 1-(2,4-dialkoxyphenyl)-3-(substituted phenyl) prop-2-en-1-one under cold conditions. On stirring, the desired dibromo derivatives were obtained. Further treatment of an ethanol solution of the dibromo derivatives with hydroxylamine hydrochloride in the presence of aqueous potassium hydroxide

Synthetic procedures for the preparation of 1-bromo-3butyn-2-one and 1,3-dibromo-3-buten-2-one were reported by Mekonne et al.84 These compounds were prepared from 2(bromomethyl)-2-vinyl-1,3-dioxolane, which was converted to 2-(1,2-dibromoethyl)-2-(bromomethyl)-1,3-dioxolane. Double dehydrobromination with t-BuOK afforded 2-ethynyl-2-(bromomethyl)-1,3-dioxolane. Formolysis with formic acid gave the first product. Deacetalized 2-(bromomethyl)-2-vinyl-1,3-dioxolane was treated with bromine and Li2CO3/12-crown-4 in THF to give the second product in moderate yield (Scheme 16). 6842


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under reflux conditions produced the isoxazoles.91 The vinylene groups in poly(p-phenylenevinylene) were brominated both completely and selectively using a Br2/CHCl3 solution.92 Squaric acid was prepared from triketene (3-acetoxy-2-cyclobuten-1-one) by bromination with bromine in ethyl acetate followed by hydrolysis (Scheme 18).93

produced 74% (Z)-1-bromo-2-(methylselanyl)ethane (Scheme 22). Scheme 22

Scheme 18

Treatment of 5-phenylalk-1-enes with bromine in chloroform, carbon tetrachloride, diethyl ether, or acetic acid at −78 °C and warming to room temperature led to the formation of an unexpected tetrahydronaphthalene in 3−55% yield along with a 45−97% yield of 1,2-dibromo-5-phenylalkanes (Scheme 23).100

Alexakis developed a pathway for the synthesis of chiral αbromo-β-alkyl ketones by using Cu catalyst. They used a chiral phosphoramidite ligand for the process. The products were obtained with excellent enantiomeric excess and good isolated yields.94 The reaction of readily available 1-substituted 2,3allenols with bromine afforded 3-bromo-3-alkenals or 2-bromo2-alkenyl ketones in good yields. This was accomplished via a sequential electrophilic interaction of Br+ with the allene moiety, a 1,2-aryl or proton shift, and an H+ elimination process (Scheme 19).95

Scheme 23

Bromination of styrene in the presence of ethylene oxide by bromine in carbon tetrachloride produced a mixture containing 85% 1-(1-(2-bromoethoxy)-2-bromoethyl)benzene and 15% 1(2-(2-bromoethoxy)-1-bromoethyl)benzene (Scheme 24), which were aminated by dibutylamine.101

Scheme 19

Scheme 24 In an attempt to synthesize sulfur pentafluoride derivatives, De Marco and Fox developed potential precursors to SF5C(O) derivatives. The derivatives were prepared through the intermediate SF5CHBrCF3, which was prepared by the reaction of the olefin SF5CHCF2 with bromine at 100 °C (Scheme 20).96

In the preparation of 2-(bromomethyl)-1,3-butadiene, ipsenol, ipsdienol, and isoprene in CCl4 were brominated with bromine in carbon tetrachloride and then reacted with benzoyl peroxide−N-bromosuccinimide (NBS) in carbon tetrachloride in the first step to give 1-bromo-2-(bromomethyl)oct-2-ene, which was reductively debrominated with Zn dust in THF to produce the desired product.102 In the synthesis of benzohomotriasterenedione, bromine was used for bromination. For this, 6,8-bis(methoxycarbonyl)benzocycloheptan-7one was treated with methyl 4-(methylperoxy)-3-oxopent-4enoate to give oxabenzohomoadamantene, benzobicyclodecatriene, and bicyclodecenedione.103 Bromination of bicyclodecenedione was carried out with bromine to give the bromo product. Debromination led to the final product. Again, in the preparation of 2,3-dibromo-2-butene-1,4-diol, molecular bromine was used by Yang et al.104 For this, bromine was added to 2-butyne-1,4-diol, and the pH was adjusted with H2SO4 to 1−3 at −5 to +1 °C for 6−9 h followed by dehydration to generate 2,3-dibromo-2-butene-1,4-diol as a crude product (Scheme 25). Ionic liquids such as [bmim][PF6], [bmim][BF4], [bmim][Br], [bmim][Cl], and [bmim][NTf2] have been found as green alternatives to chlorinated solvents for the addition of Br2

Scheme 20

In the synthesis of 7-azanorbornanes, Kapferer and Vasella used bromine for electrophilic bromination of N-acylated cyclohex-3-en-1-amines.97 They carried out the reaction with bromine in dichloromethane in the presence of Et4NBr at a temperature of −78 °C (Scheme 21). Scheme 21

α-Bromo-4-aminostyrene, an intermediate for the synthesis of RU 486 analogues, was prepared by condensation of pnitrobenzaldehyde with malonic acid, bromination with bromine, elimination, decarboxylation, reduction, and addition with HBr.98(Z)-(Alkylselanyl)alkenyl bromides were prepared in two steps from (alkylselanyl)acetylenes using palladium(0)catalyzed hydroboration−bromination.99 Thus, Pd(PPh3)4catalyzed hydroboration of ethynylmethylselane with 1,3,2benzodioxaborole followed by bromination with bromine

Scheme 25

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Scheme 26

to several alkyl- and aryl-substituted alkenes, alkynes, and dienes at room temperature.105−107 Daştan studied the bromination reaction of dibromide tricyclo[7.2.1.02,7]dodeca2,4,6,10-tetraene derivatives using elemental bromine.108 For example, bromination of (1S(R),8R(S),9S(R),12S(R))-8,12dibromotricyclo[7.2.1.02,7]dodeca-2,4,6,10-tetraene was brominated with bromine in dry chloroform at 10 °C to give a mixture of tetrabrominated products (Scheme 26). Hill studied the reaction of 1-isopropenylcarborane with N2O4, N2F4, and bromine. He reported the preparation of several new compounds and their derivatives.109 He found that when 1-isopropenylcarborane was dissolved in carbon tetrachloride containing 1 equiv of bromine and irradiated with ultraviolet light for 10 min, complete decolorization of the solution resulted, and the dibromo derivative of the compound was recovered. 3.1.2. Bromination of the Aliphatic C−H Bond Using Molecular Bromine. Bromination of aliphatic ketones was accomplished by keeping the ketone in contact with excess Br2 for 4 days with intermittent cooling. The number of Br atoms introduced equals the number of H atoms adjacent to the CO groups minus the number of CO groups.110 Bromination of 2octanone by Br2-urea-AcOH for 4 h at 18−20 °C produced 71% BrCH2COCH2R (R = pentyl) and 10% MeCOCHBrR (R = pentyl). Again, acetophenone produced 80% PhCOCH2Br, and cyclohexanone produced 69% 2-bromocyclohexanone.111 Cohen investigated the natural autocatalytic reaction between acetone and bromine (Scheme 27).112

Scheme 28

the levulinic acid in the presence of urea leads to the formation of 5-bromolevulinic acid. Reactions of 2-oxaadamantane with Br2/AlBr3, HNO3, CrO3/Ac2O, and Pb(OAc)4 introduced substituents into positions remote from the oxa bridge.117 Wei et al. provided a one-pot process for the preparation of ritodrine hydrochloride, which comprised bromination of 1-(4-methoxyphenyl)-1-propanone with Br2 to obtain 2-bromo-4′-methoxypropiophenone, followed by reaction with 4- Methoxybenzeneethanamine, hydrolysis in 48% hydrobromic acid, reduction with boron compounds, and addition of hydrochloric acid to give the product. The process has the advantages of a low cost, a short reaction time, and a high product yield.118 In the photochemical reaction for the synthesis of bromomethane, molecular bromine and methane under vacuum were added to the reactor, and finally the brominated product could be obtained.119 The photochemical bromination of CH4 was studied at 423−503 K by Kistiakowsky et al.120 and was found to proceed through the chain mechanism shown in Scheme 29.

Scheme 27 Scheme 29

Bromination of trans-2(E),3(E)-diarylcyclohexanones with bromine in carbon tetrachloride produced 41−52% 6a-bromo2(E),3(E)-diarylcyclohexanones as the major product.113 Polyfluoroalkyl α,β-enones readily added Br2 to give α,βdibromo ketones. The dibromides on treatment with K2CO3 or NEt3 were easily and regioselectively dehydrobrominated to αbromo α,β-enones in 89.5−97% yield.114 Ha et al. carried out bromination of unsymmetrical ketones with Br2 in methanol, which proceeded regioselectively in good yield at the less substituted methyl carbon. The bromination of levulinic acid using this method was followed by azidation and amination to lead to an efficient three-step synthesis of 5- aminolevulinic acid in 36% overall yield.115 Zlotin et al.116 developed another method for bromination of levulinic acid and its esters with bromine in ionic liquid (Scheme 28). This results in the formation of 3-bromo derivatives as the major product. The 5bromo-substituted isomers, which are typically formed in organic solvents, were not formed under this condition. It is likely that ionic liquids effect the enolization of ketones and create an equilibrium between two different enolic forms where the thermodynamically more stable internal enol leads to the formation of 3-bromo derivatives. However, the bromination of

Bromination of methyl bromide was analogous and 7.5−10 times more rapid in this temperature range. According to the report, HBr inhibits the bromination of methane but not of methyl bromide. Thermal bromination was studied at 570 K. and found to follow the same mechanism as the photochemical reaction, except that bromine atoms are produced thermally.The compound bromoacetonitrile was prepared by bromination of acetonitrile with bromine in the presence of HCl under photoirradiation. Thus, acetonitrile was treated with HCl and brominated with Br2 under UV irradiation to give 47.2% bromacetonitrile.121 The base-catalyzed bromination of 1,1,1trifluoropropanone or its partially brominated derivatives in organic acids rapidly gave 1,1,1-tribromo-3,3,3-trifluoropropan2-one in satisfactory yield, whereas the similar bromination in concentrated H2SO4 allowed the introduction of one or two bromine atoms and smoothly produced 3-bromo-1,1,1trifluoropropan-2-one or 3,3-dibromo-1,1,1-trifluoropropan-2one, respectively.122 (Alkoxyvinyl)phosphonates were reacted 6844


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with bromine in carbon tetrachloride with mild heat evolution to yield in 2 h a product identified as ethyl 2-bromoacetate.123 Pentacyclo[6.3.0.02,6.03,10.05,9]undecane reacted with Br2 in the presence of AlBr3 to give a 41% yield of the monobromo product.124 Utilization of brominated petroleum hydrocarbons has received considerable interest in recent times. Ijam et al.125 presented such a study for a kerosene fraction boiling between 180 and 220 °C obtained from a Kuwait oil field and having a low aromatic content. This kerosene was brominated from 6.5% to 36% bromine content in steps of approximately 0.2 mol of bromine. Bromination of poly(3-methylstyrene), poly(4methylstyrene), and poly(3,4-dimethylstyrene) was achieved with Br2 under white light.126 Monobromination of the methyl group was observed for the monomethylstyrene polymers. Organic superacids effectively catalyze the bromination of C4− 7 n-alkanes, cyclopentane, and cyclohexane. The n-alkanes yield a mixture of monobrominated products, while the cycloalkanes give only cycloalkyl bromides. Thus, bromination of cyclohexane by Br2 in CH2Cl2 catalyzed by AcCl·AlCl3 for 3 h at −20° gave 45% bromocyclohexane.127 AcBr·2AlX3 (X = Cl, Br) catalyzed the ionic bromination of C4−C7 n-alkanes, cyclopentane, cyclohexane, and exo-tetrahydrodicyclopentadiene with Br2 at −20 to +20 °C in CH2Br2 to give the corresponding monobromides as the major or only products. The cycloalkanes each produced a single product, while the remaining substrates produced a mixture of monobromides. Adamantane was inert to these conditions, but gave 1-bromoadamantane in the absence of Br2.128 Treatment of alkyl-gem-dialuminum compounds with bromine and then with water produced a mixture of alkyl bromides, 1,1-dibromoalkanes, and 1,2 dibromoalkanes.129 Treatment of 2,2-dialkyl-1,3-dioxacycloalkanes with bromine in a acetate buffer solution produced 60− 70% bromoalkyl derivatives.130 Benzonorbornadiene was brominated with bromine at 10 °C to form the 2-exo-7-antidibromide with a high yield (Scheme 30).131

Scheme 32

4. The resulting α-bromo ketones rearrange rapidly in acid solution to yield dibenzylnaphthols (Scheme 33).135 Scheme 33

The polyhalomethane·2AlBr3 aprotic organic superacids were shown to effectively catalyze low-temperature ionic bromination of (cyclo)alkanes. Ethane readily reacts with Br2 at 55−65 °C, affording mainly 1,2-dibromoethane. Propane, butane, and C5−C6 cycloalkanes (cyclopentane, cyclohexane, methylcyclopentane) react at −40 and −20 °C, resulting in monobromides with high yields and good selectivity.136 Treatment of camphene with Br2 gave dibromo and tribromo derivatives.137 (α,β-Dibromoethyl)benzenes were prepared by Tanaka et al. For example, 3-(Chloroethyl)benzene was treated with bromine and Bu4NHSO4 at 40−70 °C to give 94% 1-(1,2dibromoethyl)-4-chlorobenzene, 3-ClC6H4CHBrCH2Br. The latter was stirred with ethanolic KOH to give 99% 3-chloroα-bromostyrene.138 (Scheme 34) Scheme 34

Scheme 30

Amino-substituted aryl methyl ketones were selectively brominated in sulfuric acid to afford the corresponding dibromomethyl aryl ketones. The bromination in neat sulfuric acid completely eliminated the ring bromination, and the 2,2dibromo-4-(dimethylamino)acetophenone was obtained as the exclusive product, even when only 1 equiv of bromine was used in the reaction (Scheme 35).139

Shimada et al. reported that reaction of 3,3-disubstituted bornane-2-thiones with bromine afforded the corresponding 10-bromobornane-2-thiones (Scheme 31).132 The reactions were carried out by treating the substrate in dichloromethane at room temperature within a very short time period.

Scheme 35

Scheme 31 α-Bromo-p-hydroxyacetophenone was prepared by bromination of p-hydroxyacetophenone using Br2 in ethanolic HBr.140 (α-Bromoalkyl)arenes were prepared by bromination of alkylarenes with Br2 in aromatic hydrocarbons or aliphatic hydrocarbons in the presence of radical initiators. Thus, bromination of 4′-methyl-2-cyanobiphenyl with Br2 in PhCl in the presence of 2,2′-azobis(2-methylbutyronitrile) gave 67.2% 4′-(bromomethyl)-2-cyanobiphenyl.141 Bromination of m-chloropropiophenone was carried out with Br2 in HOAc in the presence of AlBr3/ZnBr2 catalyst to prepare m-chloro-αbromopropiophenone. At 10 °C, the m-chloropropiophenone/ Br2 molar ratio was 1:1, and the catalyst content was 1%.142 The 2,4-Dibromo-1,5-glutaraldehyde/3-(aminopropyl)triethoxysilane complex was prepared by first making 2,4-dibromo-1,5-

Treating 12-oxahexacyclo[5.4.1.02,6.03,10.05,9.08,11]dodecane with excess Br2 containing BBr3 gave a 29% yield of the bromo product.133 In the process for preparing 2-acetylresorcinol, by bromination of 2-acetyl-1,3-cyclohexanedione, the bromination step was carried out using Br2. The resulting 2acetyl-4-bromo-1,3-cyclohexanedione underwent dehydrobromination to give the product (Scheme 32).134 Reaction of dibenzyltetralone with bromine or phosphorus pentabromide results in bromination (or dibromination) at C6845


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glutaraldehyde by the reaction of glutaraldehyde with Br2 in acidic conditions and then mixing with TSC 202 at 25−80 °C and 10000 rpm for 5 min to obtain the desired salt (Scheme 36).143

Scheme 40

Scheme 36

methyl-1,3-dioxolane. In the first step of the reaction, the acetal was converted to 2-(1-bromoethyl)-2-(bromomethyl)-1,3dioxolane by reaction with elemental Br2 in CH2Cl2 to give a 98% yield. Then, following other steps, the final product was obtained.150 Aitken et al. prepared 2-bromo-1,2-diphenylpropan-1-ones by treatment of 1,2-diphenylpropan-1-one with Br2/AlCl3 (Scheme 41).151

Ziobro invented the process of preparing 4′-(bromoacetyl) methanesulfonanilide, which comprises the bromination of 4′acetylmethanesulfonanilide with Br2 in the presence of a catalytic amount of benzoyl peroxide in ethanol (Scheme 37).144

Scheme 41

Scheme 37 Again, the α-hydrogens of carboxylic acids can be replaced by bromine in the presence of phosphorus halide as the catalyst. The reaction is known as the Hell−Volhard−Zelinskii reaction (Scheme 42).152

Choi et al. reported a new synthetic method for the preparation of α-bromo ketones that are brominated in the less activated terminal position of unsymmetrical ketones using Br2 as the brominating agent (Scheme 38).145

Scheme 42

Scheme 38 Ward described the conditions for the preparation of αbromoacetic acid by the action of acetic acid and bromine in the presence of red phosphorus at 100 °C.153 The best conditions for the preparation of α-bromoacetic acid are the action of 20 g of acetic acid and 58 g of bromine in the presence of 0.4 g of red phosphorus at 100−105 °C to achieve a yield of about 80%. It was reported that bromination of camphoric acid (using 0.1 g of red phorphourous per 5 g of acid) can be achieved by carrying out the reaction at 125 °C to produce the bromo compound in 75% yield. A similar report for brominating acetic acid using bromine and red phosphorus was reported by Peng.154 Unsubstituted aliphatic carboxylic acids were α-brominated by bromine in the presence of COBr2, COBrCl, or COCl2. Thus, stearic acid in CCl4 was treated with bromine in the presence of COBr2 to give α-bromostearic acid. Similarly, a 99% yield of α-bromopalmitic acid and a 99.8% yield of α,α′-dibromoazelaic acid were prepared by using bromine in the presence of COCl2 instead of COBr2.155 Bromination of monomethyl succinate by Br2/SOCl2 afforded a mixture of bromosubstituted compounds 3-(methoxycarbonyl)2-bromopropanoic acid and 3-(methoxycarbonyl)-3-bromopropanoic acid. It is believed that a rearrangement initiated by protonation of the acid chloride carbonyl takes place during the bromination step.156 ω-Bromodehydroacetic acid was prepared by bromination of dehydroacetic acid in acetic acid with bromine at 50−70 °C.157 The reaction of a series of vinylboronic acids with bromine on alumina was examined by Willis et al. A mixture of (E)- and (Z)-vinyl bromides was formed in every case.158 3-(Bromomethyl)-4-(alkylsulfonyl)-2halobenzoic acids were prepared by the photochemical bromination of 3-methyl-4-(alkylsulfonyl)-2-halobenzoic acids using bromine.159 Tanner et al. studied the photobromination of (−)-(2R)-2-bromobutane with bromine 81. In the above reaction, chirality was maintained in the products dl-2,3-

α-Bromo(methylthio)acetophenones can be produced by treating the corresponding (methylthio)acetophenone with a brominating agent. Thus, 4-(methylthio)acetophenone was dissolved in methanol and brominated with Br2, producing αbromo-4-(methylthio)acetophenone in 98% yield.146 The action of bromine (1 equiv) on thymoquinone led to the bromination at the 6-position to form the corresponding monobromothymoquinone (Scheme 39).147 However, it was Scheme 39

found that, depending on the amount of bromine in the reaction, different bromo derivatives are obtained. For example, the action of two bromine molecules on thymoquinone gave 3,6-dibromothymoquinone, whereas, with three or four bromine molecules, a tribromide was formed. 1-(4-Acetamidophenyl)-α-bromo-1-propanone was synthesized from 1-(4-acetamidophenyl)-1-propanone by bromination with Br2 in ethanol, and the yield was 70%.148 For the synthesis of (E)-1-(4-hydroxyphenyl)-5-phenyl-2-en-1-pentanone with p-hydroxyacetophenone, in the first step Br2 was dripped slowly at −10 to +50 °C, followed by stirring at room temperature for 2 h to give 2-bromo-1-(4-hydroxyphenyl) ethanone (Scheme 40).149 A convenient procedure for the synthesis of 1-bromo-3buten-2-one was described by Carlson et al. from 2-ethyl-26846


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tolyloxy)benzene was treated with bromine gas at 255 °C and PCl3 catalyst, the reaction produced 1-(3-(bromomethyl) phenoxy)benzene and 1-(3-(dibromomethyl)phenoxy)benzene, with individual yields of 70.2% and 9%, respectively (Scheme 45).170

dibromobutane and 2,2,3-tribromobutane. The radical intermediate initially formed in the reaction was the classical 1methyl-2-bromopropyl radical, which was trapped by Br2 in its open unsymmetrical structure to yield the optically active dibromide.160 Treating β-alkenylborabicyclo[3.3.1]nonanes with H(Cl)ZrCp2 in CH2Cl2 followed by bromine regioselectively produced 83−99% yields of the corresponding αbromoboranes.161 Dibenzoylmethane and bromine produced 76% dibromodibenzoylmethane with sodium acetate. In acetic acid, 86% dihydroxydibenzoylmethane resulted, and on distillation, 91% dibenzoylmethanone was produced (Scheme 43).162

Scheme 45

A similar reaction for synthesis of a mixture of 3phenoxybenzyl bromide and 3-phenoxybenzal bromide was obtained by brominating 1-(m-tolyloxy)benzene with 1.3−1.5 mol of Br2 at 195−235 °C in the presence of an inert gas and in the absence of radiation, a catalyst or initiator, and solvent.171,172 Sket and Zupan developed a bromine complex of poly(styrene-co-4-vinylpyridine) for side chain bromination of aromatic molecules.173 Reaction was carried out by treating a mixture of alkylbenzene, benzoyl peroxide (BPO), and the supported bromine reagent under reflux conditions for 3−4 h to yield the corresponding bromo derivative in over 90% yield. Baciocchi et al. carried out photochemical bromination of benzyltrimethylsilanes in carbon tetrachloride or acetic acid with Br2 to give (bromophenyl)trimethylsilane, whereas similar photobromination in AcOH/CF3CO2H gave a mixture of 15% (bromophenyl)trimethylsilane and 52% benzyl bromide.174 Photobromination of (4-methoxybenzyl)trimethylsilane with Br2 in acetic acid gave 4-methoxylbenzyl acetate. Tanko et al. introduced a new bromination method with molecular bromine in supercritical CO2. Free radical side chain brominations of alkylaromatics in supercritical carbon dioxide (SC-CO2) were very good. Direct bromination of toluene and ethylbenzene gave the corresponding benzyl bromides in high yield. The observed selectivity in SC-CO2 was similar to that observed in conventional organic solvents, and SC-CO2 became an effective alternative to carbon tetrachloride (Scheme 46).175

Scheme 43

Kochetkov et al. carried out the bromination of β-oxo acetals by addition of Br2 to oxo acetal and BaCO3 in water under an incandescent lamp, finally at 40−50 °C, to give α-bromo-β-oxo aldehydes.163 CHCl3 was brominated with bromine in the ratio 1.25:1 at 300−320 °C in a packed reaction column to give trichlorobromomethane.164 Treatment of 1-bromo-1-fluoroalkanes with bromine at 500−700 °C produced dibromofluoroalkanes. Thus, feeding an equimolar mixture of bromofluoromethane and bromine to a quartz reactor at 600 °C and a flow rate of 300 mL/min gave 83% dibromofluoromethane.165 Trifluorobromomethane was prepared by bromination of trifluoromethane with Br2 in the presence of chlorine in the gas phase and at a temperature of 500−600 °C, with prior mixing of the reagents.166 The Ni(II) chelate complexes also undergo bromination at the methyne carbon atom in the presence of bromine in chloroform.167 When 2-furyl methyl ketone in carbon disulfide was brominated at, or below, room temperature by the dropwise addition of bromine in carbon disulfide, both the first and second bromine atoms entered the side chain, forming (a) 2-furyl bromomethyl ketone or (b) 2furyl dibromomethyl ketone (Scheme 44).168 The yield was found to be 90% in both cases.

Scheme 46

Scheme 44 2-Bromo-1-(meta-substituted phenyl)ethanol was prepared by Tanaka176 by bromination of meta-substituted ethylbenzene, XC6H4Et (X = halo, NO2, cyano, CF3) over quaternary ammonium sulfate and the following hydrolysis in the presence of iodides and phase transfer catalysts. Li et al. prepared pcyanobenzyl bromide by bromination of p-methylbenzenenitrile with H2O2−Br2 under photoirradiation in the cyclohexane solvents, giving the product with a yield of 82% in 99% purity (Scheme 47).177 2-Bromo-4′-methoxyacetophenone was synthesized by adding a methanolic solution of bromine to a solution containing

When 5-bromo-2-furyl methyl ketone was brominated, the bromine entered the side chain with 50% yield. No nuclear bromination was found in any of these cases. 1-(2Hydroxyphenyl)ethanone and similar ortho- and para-substituted ketones undergo predominantly side chain substitution with bromine in anhydrous acetic acid and nuclear substitution in aquous acetic acid. However, ketones of high molecular weight undergo only nuclear monobromination.169 When 1-(m-

Scheme 47

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reaction was carried out in a mixed solvent consisting of CCl4 and H2O by treating the substrate with bromine to produce 1(bromomethyl)-2-nitrobenzene, and then further reaction led to the final product. Bromofluorobenzenes were prepared by bromination in the presence of iodine, a metal, or a metal salt as the catalyst.184 For example, treatment of bromine with a mixture of AlCl3 and 1(4-fluorophenyl)ethanone to dichloroethane/Br2 at 45 °C over 4 h produces bromofluoroacetophenone in 79% yield. Baciocchi et al.185 showed that diethyl 3,4-dimethylpyrrole2,5-dicarboxylate and diethyl 3-ethyl-4-methylpyrrole-2,5-dicarboxylate smoothly react with bromine in CCl4 at 70 °C. Diethyl 3,4-dimethylpyrrole-2,5-dicarboxylate always forms a mixture of diethyl 3-(bromomethyl)-4-methyl-1H-pyrrole-2,5-dicarboxylate and diethyl 3,4-bis(bromoethyl)-1H-pyrrole-2,5-dicarboxylate, while with diethyl 3-ethyl-4-methylpyrrole-2,5-dicarboxylate the monobromo derivative diethyl 3-(bromomethyl)-4ethyl-1-H-pyrrole-2,5-dicarboxylate is exclusively produced (Scheme 53). Interestingly, the ethyl substituent was not affected during the bromination reaction.

4′-methoxyacetophenone and concentrated hydrochloric acid in methanol for 6 h and continuing the reaction for another 1 h at room temperature and for 2 h in an ice bath (Scheme 48).178 Scheme 48

Another method for the synthesis of 3-(aryloxy)benzyl bromides was reported whereby 3-(aryloxy)toluenes were treated under UV irradiation and with an equimolar amount of bromine at 220 °C for 30 min, with a N2 carrier (Scheme 49).179 However, the reaction produced a small amount (2%) of ring-brominated product. Scheme 49

Scheme 53 Drake and Bronitsky reported a method for α-bomination of acetophenone.180 They achieved the synthesis by treating 1-(4phenyl)ethanone with molecular bromine in acetic acid to produce p-phenylphenacyl bromide in high yield (Scheme 50). Scheme 50

A method of preparation of 4-(trifluoromethyl)aniline was reported by Qiu, where in the first step 4-nitrotoluene was brominated with bromine to obtain 4-(dibromomethyl)nitrobenzene (Scheme 54).186

A method for monobromination of carbonyl compounds belonging to cyclic and acyclic ketones, amides, and β-keto esters was developed by Das using NBS as the bromine source (Scheme 51).181 The reaction was carried out by treating the

Scheme 54 Scheme 51

carbonyl compound with NBS in the presence of silicasupported sodium hydrogen sulfate (NaHSO4·SiO2). In general, cyclic ketone or β-keto esters could be brominated at room temperature, whereas acyclic ketones or lactams need a high temperature (80 °C) to drive the reaction forward. In all cases, the α-monobrominated products were obtained in high yield. Schulze and Stritzke described a process for the side chain bromination of alkylbenzenes using bromine.182 In a process for the preparation of o-nitrobenzaldehyde, bromination of 1methyl-2-nitrobenzene was carried out (Scheme 52).183 The

Chou et al.187 described a method for producing 1,4bis(bromodifluoromethyl)tetrafluorobenzene (BFTFB) where molecular bromine was used for bromination of 1,4bis(difluoromethyl)tetrafluorobenzene (DFMTFB), under UV radiation at 100−200 °C. In the first step of synthesis of the compound 2-bromo-6-fluorobenzyl alcohol, bromination was carried out with 2-bromo-6-fluorotoluene using molecular bromine under illumination to obtain 2-bromo-6-fluorobenzyl bromide.188 In the preparation of N-(2,3-dichloro-6-nitrobenzyl)glycine ethyl ester, Lang used bromine for bromination of 2,3-dichloro-6-nitrotoluene in the presence of benzoyl peroxide in CCl4.189 4-(1-Adamantyl)benzyl bromide was prepared by brominating p-tolyladamantane with Br2 at 45− 50 °C in CCl4 containing perfluoroenanthic acid peroxide initiator (Scheme 55).190 Bromomethyl-substituted aromatic carboxylic ester compounds were prepared by reaction with bromine in the

Scheme 52

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with amines and with CN− were also studied during the course of this investigation. Lourens et al. prepared (bromomethyl) dioxolanes by treatment of the methyldioxolane precursor with bromine.201 Thus, 2-(2,4-dichlorophenyl)-2-methyl-4-propyldioxolane in toluene at 35 °C was treated with bromine over 4 h to give 2-(bromomethyl)-2-(2,4-dichlorophenyl)-4-propyldioxolane (Scheme 58). This was heated with 1,2,4-triazole potassium salt and potassium carbonate in DMF to give propiconazole.

Scheme 55

presence of a free radical initiator, an oxidizing agent, and water. Thus, reaction of tert-butyl 4′-methylbiphenyl-2carboxylate with Br2 in water and EtOAc in the presence of 2,2′-azobis(isobutyronitrile) (AIBN) and sodium bromate at 50 °C for 1 h produced 76.9% tert-butyl 4′-(bromomethyl) biphenyl-2-carboxylate (Scheme 56).191

Scheme 58

Scheme 56

12-Bromodehydroabietic acid and 12-(bromomethyl)dehydroabietate were synthesized with three bromide system methods, the bromine−acetic acid, NBS, and Br2−MnO2 systems, respectively.202 The study demonstrated that, in comparison with the other two systems, the reaction time of the Br2−MnO2 system was shorter, its synthetic cost was cheaper, and it had higher selectivity and higher yields. Moreover, the reaction proceeds in mild conditions, and its operation is simple. Cinquini carried out reaction of sulfoxides with bromine in the presence of pyridine to produce α-bromo sulfoxides.203 This α-bromo sulfoxides were oxidized further by m-chloroperbenzoic acid in dichloromethane (DCM) to give αhalo sulfones. The ω-brominated α-(trifluoroacetyl)cycloalkanones and their isoxazole derivatives were synthesized by Flores et al. (Scheme 59).204 The reaction of a series of the 2-

Ethylbenzene was reacted with bromine under UV irradiation to synthesize (α-bromoethyl)benzene, and the (α-bromoethyl) benzene was sulfonated by fuming sulfuric acid, dehydrobrominated, and then salted out to obtain p-styrene sodium sulfonate.192 Spencer described the action of bromine on sodium and silver azides.193 In the absence of water Br2 reacted with NaN3 and AgN3 to give the highly unstable bromoazoimide. Bromine produces HN3 and HBrO by reaction with NaN3, which then interacts to form N2. When more NaN3 was present than required for the reaction, evolution of N2 was more rapid because of the interaction of HBrO with NaN3, so that 2 equiv of Br2 decomposes 2 equiv of NaN3. The addition of Br2 to γ-chloroallyl phenyl ether in equimolar amounts in CHCl3 at 0 °C gave γ-chloroallyl bromide, phenol, pbromophenol, and γ-chloroallyl p-bromophenyl ether.194 αBromo dimethyl acetals were obtained in excellent yields by treating dimethyl acetals with Br2−NaBr−chlorotrimethylsilane in CH3OH/CH3CN (2:1).195 Bromination of 2-alkyl-4-oxo1,3-benzoxazinium perchlorates was done with Br2/AcOH to give the 2-bromomethyl derivative, which was resistant to further bromination.196 Bromination of 1,3-dialkylperimidones by Br2 in acetic acid gave the monosubstituted product.197 Perfluorobromoalkane and/or perfluoroalkane are synthesized by the reaction of perfluoroalkyl iodide with Br2 in the presence of an iodine-absorbing substance at 0−150 °C and 10−100 kPa under illumination with a low-pressure mercury lamp (220− 260 nm).198 Liu et al. provided a process for the preparation of 2-substituted 4′-(bromomethyl)biphenyls, which included bromination of 2-substituted 4′-methylbiphenyls with bromine in an organic solvent under sunlight (Scheme 57).199 The reaction proceeds within a short time to produce 4′(bromomethyl)biphenyls in high yield. Secondary and tertiary enamines having an α-methyl group and a β-hydrogen were brominated using bromine.200 The secondary enamines were brominated at the β-position; the tertiary enamines were brominated on the α-methyl group. Further reactions of the α-(bromomethyl) tertiary enamines

Scheme 59

(trifluoroacetyl)-1-methoxy-1-cycloalkenes and 2-(trifluoroacetyl)cycloalkanones with bromine to obtain ω-bromo-α(trifluoroacetyl)cycloalkanones was reported. Bromination of ethyl 2-butyl-2-cyano-4-methyl-5-oxohexanoate by Br2−CCl4 gave an intermediate 4-bromo derivative, which was treated with sodium acetate and acetic acid to give 58% pyrrolidinone.205 2,6-Diamino-4,5,6,7-tetrahydrobenzothiazole, the intermediate in the preparation of pramipexole, was prepared in a one-pot synthesis by bromination of 4acetamidocyclohexanone with bromine in water and then adding the other reagents.206 Again a process for synthesizing raloxifene hydrochloride proceeded by treating 4-methoxyacetophenone with bromine followed by reaction of the brominated intermediate with 3-methoxybenzenethiol, and then subsequent reactions were followed.207 A process for the preparation of propiconazole was invented, where cyclization of 2,4-dichloroacetophenone with 1,2-pentanediol in the presence of solid heteropoly acid catalyst was performed, followed by

Scheme 57

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bromination with Br2 and condensation with 1,2,4-triazole in the presence of K2 CO 3 .208 Alexander et al. prepared morpholinobenzothiazoles and related compounds. For example, spiro[4,5]decane-7,9-dione in acetic acid was treated dropwise with bromine to give a crude product which was heated with morpholine-4-carbothioamide and diisopropylethylamine in THF to give 2-(morpholin-4-yl)-4H-spiro[1,3benzothiazole-5,1′-cyclopentan]-7(6H)-one (Scheme 60).209

Scheme 63

in carbon disulfide followed by addition of bromine in proportions at low temperature (5 °C) (Scheme 64). The Scheme 64

Scheme 60

reaction is very selective and produces the p-bromophenol exclusively in high yield. Takechi and Fukai found that pbromophenols can be prepared regioselectively in 91% yield by carrying out the bromination reaction in 1,2-dimethoxyethane using bromine for 5 h at room temperature.216 Similar results can also be obtained if the bromination is carried out in a mixed solvent consisting of acetic acid and water in the presence of tetramethylammonium bromide at 25 °C for 2 h.217 In 1927, Varma et al. studied the bromination of benzene with bromine in the presence of concentrated H2SO4, fuming H2SO4, HNO3, O2NSO3H, etc.218 Jakes found that 1,3dibromo-2-tetralol undergoes reaction with bromine to yield a mixture of 3,6-naphthol and 3,7-dibromo-2-naphthol. An interesting feature of this reaction is that the bromine in position 1 was lost during the reaction.219 Wheeler and Ergle studied the bromination of 1,5-dihydroxynaphthalene with bromine.220 Treatment of 1,5-dihydroxynaphthalene and 2 mol equiv of bromine in acetic acid at 80 °C produced the 2,6dibromo derivative in 76% yield (Scheme 65).

In the preparation of o-glycosyl nitrone compounds, carbohydrates were reacted with acetic anhydride to obtain peracetylated carbohydrates, followed by bromination with bromine in the presence of red phosphorus, glycosylation with hydroxy-containing aromatic aldehydes, and reaction with Nsubstituted hydroxylamines to give the products.210 A process for selectively producing 4,9-dibromodiamantane comprises the reaction of diamantane with bromine in the presence of AlBr3 in cyclohexane over 2 h to obtain a 70% yield of the product.211 Cyclocondensation of (triethylsilyl)azomethane with (triethylsilyl)formaldehyde at room temperature produced (Z)-2,3bis(triethylsilyl)cyclopropanone, which was then brominated with bromine in dichloromethane at −78 °C to give 1,3dibromo-1,3-bis(triethylsilyl)propan-2-one in 96% yield (Scheme 61).212 Scheme 61

Scheme 65

In the process for the preparation of substituted triazolylalkyl pyridyl ethers, bromine was used for bromination.213 In this process 4-hydroxy-3,3-dimethylbutan-2-one was successively tosylated in pyridine, and the tosylate was added to KF in tetraethylene glycol to produce the fluoro derivative. Then the resulting 4-fluoro-3,3-dimethylbutan-2-one was brominated with bromine in diethyl ether to give 1-bromo-3-(fluoromethyl)-3-methylbutan-2-one (Scheme 62).

Bromine in glacial acetic acid in the presence of sodium acetate is also successfully applied with 2-naphthol to prepare 2,2,4,7-tetrabromonaphthalen-1(2H)-one.221,222 A similar approach for the halogen derivatives of acyl and alkyl resorcinols was also reported by Brewster and Harris. For example, reaction of resacetophenone and bromine in acetic acid at reflux temperature led to the bromination of both the aromatic ring and the α-position of the carbonyl group. They isolated ωdibromo-3,5-dibromo-2,4-dihydroxyacetophenone from the reaction of resacetophenone and bromine under this condition (Scheme 66).223 In the synthesis of 3,6-dimethoxy-2-naphthaldehyde, first, 2,7-dihydroxynaphthalene was treated with bromine in acetic acid to give 55% and 26% yields of the isomeric dibromodihydroxynaphthalenes. Further synthetic manipula-

Scheme 62

A method for the preparation of bromofurylbutenone has been described by Saikawa and co-workers.214 The synthesis was achieved by treating 1-(furan-2-yl)but-3-en-2-one in THF containing BF3·Et2O with bromine at 40−45 °C (Scheme 63). The reaction produced the corresponding bromofurylbutenone in 68% yield. 3.1.3. Aromatic Ring Bromination Using Molecular Bromine. Adams and Marvel developed a procedure for the preparation of p-bromophenol from phenol using elemental bromine.215 They carried out the reaction by dissolving phenol

Scheme 66

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tion of the resulting dibromo products could produce the final product.224 6-Bromo-2-naphthol was prepared by bromination of 2-naphthol with bromine in methanol at 35 °C, followed by debromination of the resulting 1,6-dibromo-2-naphthol using alkali-metal sulfites.225 Brenans prepared 6-bromo-2,4-diiodophenol and 4-bromo-2,6-diiodophenol by the action of bromine in acetic acid on 2,4- and 2,6-diiodophenol, respectively (Scheme 67).226

Scheme 69

thylbenzene produced 90% 3-bromo-1-methoxy-2,6-dimethylbenzene and 90% 3,5-dibromo-1-methoxy-2,6-dimethylbenzene using different bromine/substrate ratios.233 In the regiospecific alkoxylation of phenolic aldehydes by Puri et al, vanillin was brominated with bromine in acetic acid to give 5-bromovanillin, which was subsequently methylated to give 5-bromoveratraldehyde.234 However, Afanaśeva and coworkers developed a different procedure for the synthesis of the same substrate. They achieved the synthesis of 5-bromovanillin by treating vanillin with bromine in 1-ethyl-3-[3-(dimethylamino)propyl]carbodiimide (EDC) containing 55% H2SO4 followed by treatment with 30% H2O2 at 45 °C to produce the desired product in 99% yield (Scheme 70).235

Scheme 67

Heller and co-workers studied the action of bromine on phenol.227 They divided the action of bromine on phenols into several categories, and according to the reaction type, different products were obtained. For example, when N-(5-hydroxy-2,4dinitrophenyl)acetamide reacts with bromine in acetic acid at 100 °C, it produces 4,6-dinitro-3-amino-2-bromophenol. Brink investigated the bromination of some phenolic alcohols.228 Bromination of these compounds in acetic acid or in chloroform produced different brominated products depending on the amount of bromine used. Again the ortho bromination of phenol can be achieved using elemental bromine at low temperature.229 It was found that the action of bromine on phenol in the presence of tert-butylamine in toluene at −70 °C produces the ortho-brominated product in high yield. Depending on the amount of bromine, mono- or dibromination can be achieved using this procedure (Scheme 68).

Scheme 70

3,5-Dibromo-4-hydroxybenzonitrile, bromoxynil, has been synthesized in two steps from p-cresol. p-Cresol was brominated first by Br2 and then treated with nitroethane/ fused sodium acetate in acetic acid to give bromoxynil.236 Yang et al. synthesized 3,5-dibromo-4-hydroxybenzaldehyde from pcresol and o-dichlorobenzene in a bromination reactor, keeping the temperature at 32−42 °C and dropping bromine to perform bromination for 4−5.5 h.237 Reaction of p-hydroxybenzoic acid using 2.5 mol equiv of bromine in acetic acid at 90−110 °C results in the formation of 3,5-dibromo-4hydroxybenzoic acid in 80% yield (Scheme 71).238

Scheme 68

Scheme 71

Selection of the solvent has been found to be the crucial parameter for the selectivity. For example, a method for selective synthesis of p-bromophenol was reported by Becker, where they carried out the bromination of phenols with bromine at −20 to +50 °C in different esters as solvents.230 Chalabiev et al.231 improved the process of producing dibromophenol via bromination of phenol by use of bromine and 16−25% aqueous sodium hypochlorite or 25−30% aqueous hydrogen peroxide as the oxidizing agent. The bromination of p-bromophenol using iodine and anhydrous aluminum chloride as catalysts was studied by Rajaram et al.232 The effective reaction conditions are found to be either a combination of iodine bromide in acetic acid and carbon tetrachloride or a combination of aluminum chloride and bromine in acetic acid. Reaction of bromine with 2,6dimethylphenol in SbF5−HF produced 85% 3-bromo-2,6dimethylphenol, whereas further bromination produced 85% 3,4-dibromo-2,6-dimethylphenol and 5% 3,5-dibromo-2,6dimethylphenol (Scheme 69). Similarly, 1-methoxy-2,6-dime-

Hodgson239 found that bromination of m-hydroxybenzaldehyde in water produces a mixture of bromo products. However, careful addition at 50 °C can produce the pure 2,4,6-tribromo derivative exclusively. Olah and co-workers found that ring bromination of benzene and alkylbenzenes can be achieved by carrying out the reaction using bromine in nitromethane in the presence of ferric chloride as the catalyst at room temperature.240 This procedure has the advantage of high positional selectivity. Tishchenko241 studied the bromination of aromatics in an aqueous solution with bromine. Using this procedure, naphthalene could be converted to pure α-bromonaphthalene in 80% yield (Scheme 72). Similarly, phenol could be transformed into p-bromophenol in 70% yield. Tribromophenol could be produced under alkaline conditions. For example, when phenol (4 g) was treated with bromine (20 g) in the presence of sodium carbonate (36 g), tribromophenol was obtained (Scheme 73). Similarly, m- and o-cresols gave 84% 6851


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none imines depending on the solvent, temperature, and molar ratio of starting material to bromine.248 A method of synthesis of 3,3′,5,5′-tetrabromo-2,2′-dihydroxybiphenyl from 2,2′-dihydroxybiphenyl was developed using a multistep sequence.249 The method comprises partial bromination of 2,2′-dihydroxybiphenyl with bromine below 35 °C at the initial phase, followed by bubbling Cl2 at 35−45 °C, and bromination of the intermediate product at 60−70 °C (Scheme 75).

Scheme 72

Scheme 73

Scheme 75 and 70% yields, respectively, of the 6-bromo derivative; p-cresol produced a 60% yield of the monobromo derivative under the same reaction conditions. Firouzabadi et al. reported that heteropoly acid cesium salt/ cetyltrimethylammonium bromide could highly control regioselective bromination of aromatic compounds with bromine.242 They reported a procedure for regioselective monobromination of phenol and its derivatives and some aromatic compounds with bromine in the presence of a heterogeneous catalytic system composed of Cs2.5H0.5PW12O40 and cetyltrimethylammonium bromide (CTAB). Bagli and Écuyer developed a procedure for the synthesis of 2,5-dibromobenzoquinone by treatment of hydroquinone with bromine followed by oxidation with iron(III) chloride.243 However, this procedure is not efficient as the product was obtained in low yield. In a different approach, treatment of 1,4-benzoquinone with 2 mol equiv of bromine in a mixture of ether and chloroform at room temperature followed by successive treatment with sulfuric acid and Ag2O could produce 2,3-dibromo-l,4-benzoquinone in 68% yield (Scheme 74).244

Hodgson and co-workers studied the bromination of 6-nitro1-naphthylamine with bromine to synthesize 2,4-dibromo-6nitronaphthalen-1-amine (Scheme 76), which was further Scheme 76

diazotized with NaNO2 to produce 1,3-dibromo-7-nitronaphthalene.250 Further treatement of the diazo solution with cupric bromide could produce 1,2,4-tribromo-6-nitronaphthalene in high yield. Jadhav et al. studied the bromination of arylamides of 2methoxy-5-nitrobenzoic acid with molecular bromine. The pbromo and 2,4-dibromo products were obtained under this reaction condition.251 Patakoot et al. studied the bromination of some arylamides of 2-hydroxy-4-methylbenzoic acid (mcresotic acid). With molecular bromine, higher bromo derivatives in both nuclei were obtained.252 Bromination of the (nitronaphthyl)amines and of their N-acetyl and Narylsulfonyl derivatives under a variety of conditions was studied using molecular bromine. (Nitronaphthyl)amine could be transformed into the corresponding monobromo or dibromo derivative in cold CHCl3 at room temperature using a 10% solution of bromine in CHCl3. It was found that the addition of 8.6 mL (per gram of the substrate) of bromine solution results in monobromination, whereas the addition of 17.1 mL can effect dibromination of nitronaphthylamine.253 Bromination of nitrohydroxyacetophenones in acetic acid produced ring-substituted compounds, while the corresponding phenacyl bromides were obtained in acetic acid or in CHCl3 in the presence of sodium acetate.254 4-Bromo-1-(methylamino) anthraquinone was prepared by Chalykh et al. 255 by brominating 1-(methylamino)anthraquinone with bromine in dichloromethane. Bromination of 4H-cyclopenta[def ]phenanthren-1-amine, -2-amine, -3-amine, or -8-amine with bromine in chloroform took place at the 2-, 1-, 8-, or 9position, respectively (Scheme 77). The second bromine could be introduced at the 8-, 3-, 2-, or 3-position. Similar

Scheme 74

Newman and co-workers developed a method for the synthesis of dienones from o-, m-, and p-cresol.245 Initially, they obtained di- and polybromophenols by reacting cresol with bromine in aqueous (90%) acetic acid at room temperature for 0.5 h. The polybrominated product was isolated and treated again with bromine in acetic acid at room temperature to produce the bromo dienones in good yield. 3,5Dibromo-1-methoxy-4-aminobenzene was prepared by the action of bromine on p-anisidine in alcohol without any catalyst at ordinary temperature and pressure. The action of bromine on N-(4-methoxyphenyl)acetamide in glacial acetic acid yielded 3,5-dibromo-1-methoxy-4-acetamidobenzene.246 In the intermediate step of the synthesis of anthranilic acids, bromine was used as the brominating agent. Thus, 3,4dimethylaniline was acylated with acetic anhydride, brominated with bromine and hydrogen peroxide, and carbonylated in the presence of carbon monoxide, triphenylphosphine, and (PPh3)2PdCl2 to produce 2-(acetylamino)-4,5-dimethylbenzoic acid.247 Bromination of N-acyl derivatives of p-aminophenols, 4-amino-1-naphthols, and p-phenylenediamines was carried out with bromine to produce N-acyl-2-bromo-4-aminophenols, Nacyl-2,6-dibromo-4-aminophenols, N-acyl-2,3,6-tribromo-4aminophenols, and N-acyl- 2,3,5,6-tetrabromo-1,4-benzoqui-

Scheme 77

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regioselectivity was observed in the system of bromine in acetic acid−48% HBr and HBr in DMSO. The corresponding acetamido compound was brominated at the same position as that of the parent amine.256 6-Bromo-2,4-dinitroaniline was prepared by brominating 1 mol of 2,4-dinitroaniline with 0.5 mol of bromine with subsequent additional bromination through the action of NaOCl, resulting in a low bromine content in the wastewater (Scheme 78). On addition of NaOCl to the reaction mixture, HBr formed during the initial bromination was oxidized to Br2 for the postbromination.257

Scheme 81

reaction conditions 1-(4-aminophenyl)ethanone produces ωbromo-3,5-dibromo-4-aminoacetophenone in 96% yield. Photochemical bromination of the former with Br2 also produced a 68% yield of ω-chloro-3,5-dibromo-4-aminoacetophenone.263 Brominated substituted anilines were prepared in high yield and selectivity using bromine in an aqueous medium. When a mixture of 4-amino(trifluoromethoxy)benzene and water was treated with Br2, 4-(trifluoromethoxy)-2,6-dibromoaniline was obtained in 95% yield with 99% purity.264 Smith et al. reported a process for regioselective one-pot bromination of aromatic amines via in situ formation of tin amide. Initially, aniline was treated with n-butyllithium and subsequently with trimethyltin chloride to produce PhNH−SnMe3. Without isolation of the tin amide, the reaction mixture was further treated with bromine followed by a workup using aqueous potassium fluoride solution to result in exclusive formation of pbromoaniline in 76% yield (Scheme 82).265 An important aspect of this process is that neither dibromoaniline nor obromoaniline was formed during the reaction.

Scheme 78

Treatement of 2,2′,4,4′-tetrabromodiphenylamine (50 g) with Br2 (100 mL) in dibromoethane (250 mL) in the presence of FeBr3 (5 g) produces a mixture of polybrominated product containing hepta- and octabromodiphenylamines as the major constituents.258 Bromination of 2-(tert-butyl-NNO-azoxy)anilines yields the corresponding 4-bromo and 4,6-dibromoanilines.259 4-Bromo-3-methylanilines were prepared in 60−70% yields by a one-pot method in which m-toluidine was first pretreated with sulfuric acid, then brominated with Br2, and finally neutralized with NaOH to give the desired products (Scheme 79).260

Scheme 82

Scheme 79

Again, when aniline was successively treated with n-BuLi, B(OMe)3, and Br2 at −78 °C, 4-bromoaniline was formed. The one-pot, three-stage approach (lithiation, boron amide formation, and bromination) proved to be highly useful in mildly brominating a variety of arylamines in up to 94% yields (Scheme 83).266

Zhou and co-workers developed a procedure for the synthesis of 3,5-dibromo-o-phenylenediamine from 2-nitroaniline.261 They carried out the bromination of 2-nitroaniline with bromine in acetic acid to produce 3,5-dibromo-2-nitroaniline in 38% yield (Scheme 80). Subsequent reduction of the resulting

Scheme 83

Scheme 80

Environmentally benign solid-state bromination of anilines and phenols with gaseous bromine and solid bromination reagents was described by Toda et al. In most cases the reactions proceeded in the absence of solvents with higher yields and selectivity than in solution (Scheme 84).267 Jichao prepared tribromoaniline by bromination of aniline with Br2 in chlorobenzene/urea/water, followed by oxidization of the byproduct HBr to Br2 with hydrogen peroxide solution and continuous reaction. The process has the advantages of simple procedures, >95% product yield, 98% purity, less

3,5-dibromo-2-nitroaniline with SnCl2 in concentrated HCl followed by treatment with 10% aqueous KOH produced 3,5dibromo-o-phenylenediamine. Vibhute and Jagdale studied the kinetics of bromination of different substituted phenols with molecular bromine in acetic acid and found the reactivity trend to be in the following order:262 o‐cresol > phenol > m‐chlorophenol > o‐chlorophenol > o‐bromophenol > p‐chlorophenol > salicylic acid

Scheme 84

> vanillin

Reaction of 1-(4-aminophenyl)-2-chloroethanone with bromine in acetic acid produces ω-chloro-3,5-dibromo-4-aminoacetophenone in 85% yield (Scheme 81), whereas under similar 6853


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consumption of Br2, no waste acid discharge, and a low cost.268 BeBr2 was found to be an active catalyst in the reaction between bromine and benzene. With excess bromine, p-dibromobenzene in 41% yield and tribromobenzene in 83% yield were obtained. In the presence of BeBr2 and bromine, bromobenzene could be transformed into p-dibromobenzene.269 Buckles carried out reactions with aromatic compounds using bromine vapor.270 Bromine was added to the double bond of an aryl olefin and also to the para positions of unsubstituted phenyl groups. Aromatic compounds with no olefinic double bonds also underwent bromination in the presence of bromine vapor. Interestingly, a number of compounds with more highly substituted double bonds did not undergo bromine addition, but underwent substitution in the para positions of the phenyl groups (Scheme 85).

product. When this process was extended to ethylbenzene and cumene, similar results were obtained. Highly selective ring bromination of alkyl-substituted aromatic hydrocarbons was achieved using molecular bromine adsorbed on the surface of alumina without any solvent. Thus, toluene was brominated by bromine on the surface of alumina to give a 65:35 mixture of brominated derivatives. The bromination of cumene gave 88% p-bromo derivatives.277 Reaction of o-xylene with Br2 in dichloromethane under darkness in the presence of FeBr3 catalyst at −65 to +20 °C afforded a mixture of 3,4-dimethylbromobenzene and 2,3dimethylbromobenzene with preferential formation of the 3,4adduct (Scheme 87).278 However, formation of a mixture of dibromoxylenes in small amounts was also found. Scheme 87

Scheme 85

Kulawski et al. provided a method for preparing aromatic compounds substituted by four or more bromine atoms in the ring by reaction of an aromatic substrate with Br2 in CHCl3 where the aromatic substrate was added gradually to the reaction medium consisting of solvent, catalyst (AlCl3 or AlBr3), and bromine and chlorine in 5−100% molar excess at 283−323 K. Compounds undergoing complete bromination in this way were C6H6 and its aryloxy, hydroxy, and halogenated derivatives.279 Bromination of 1,3-difluorobenzene with Br2 in the presence of iron powder at 20 °C for 24 h gave 90% 2,4difluorobromobenzene.280 Zhao et al. found that the use of iron powder is helpful in producing 1-bromo-4-methoxy-2-methylbenzene as the main product from 3-methoxytoluene using Br2 in CCl4 in at −10 °C.281 3,5-Di-tert-butylbromobenzene was prepared conveniently from the reaction of benzene with tertbutyl chloride in the presence of AlCl3, producing 1,4-di-tertbutylbenzene, followed by bromination with bromine in the presence of AlCl3.282 Li et al. described a reaction of p-xylene with bromine in the presence of Fe filings at room temperature to produce 2-bromo-p-xylene (Scheme 88).283 4-Bromoph-

Direct bromination of a wide range of aromatic compounds with electron-donating groups such as methoxy, hydroxy, or amino groups was achieved with high regioselectivity and excellent yields with bromine in the presence of oxylylenebis(triphenylphosphonium) peroxodisulfate as an oxidant under mild reaction conditions in acetonitrile.271 Li et al. developed a method for the synthesis of 2,4,6tribromostyrene where bromine was used in the presence of a catalyst.272 A different protocol has been realized by Hashem for bromination of aromatic compounds using bromine in chlorosulfonic acid medium.273 For example, treatment of disubstituted benzenes with bromine in chlorosulfonic acid produces exclusively the brominated products with no ring oxidation. Compounds containing CHO, CO2H, NO2, and CN groups underwent brominolysis to give bromobenzene derivatives. A combination of Br2, SbF3, and HF was used by Jacqesy et al.274 as a brominating mixture for activated aromatics. A convenient preparation of perbromo aromatic compounds containing electronegative groups, based on exhaustive bromination of their precursors with bromine in concentrated sulfuric acid or oleum in the presence of mercuric oxide at 35−60 °C, was presented by Shishkin et al.275 Clays and clay-based reagents were also used as catalysts for bromination reactions in organic synthesis. Selective bromination of alkylbenzenes with bromine in carbon tetrachloride in the presence of K10-montmorillonite was reported by Pitchumani et al.276 Bromination of toluene using bromine in carbon tetrachloride at room temperature gave benzyl bromide as the exclusive product. However, with bromination under similar conditions in the presence of K10-montmorillonite, a mixture of o-bromotoluene and p-bromotoluene was obtained (Scheme 86). The remarkable feature of this bromination was the absence of benzyl bromide, the side-chain-brominated

Scheme 88

thalic anhydride was prepared from phthalic anhydride using the same procedure. Under the optimum conditions, the yield of 4-bromophthalic anhydride was 75%.284 α-(Aminomethyl)4-hydroxy-1,3-benzenedimethanol was synthesized by Zhang et al., where, in one step, they used bromine to synthesize an intermediate bromo compound.285 Bromination of 9,10-anthraquinone in oleum using excess Br2 in the presence of an oxidant (H2O2, MnO2, I2, etc.) at temperature above 80 °C gives rise to a mixture of polybromoanthraquinones containing 66−73% bromine. In this process, the mono- and dibromoanthraquinones formed in situ undergo further bromination much faster than anthraquinone.286 Methyl 5-bromo-6-methoxy-1-naphthoate was prepared by treatment of methyl 6-methoxy-1-naphthoate (1 mol) with bromine (0.5−0.6 mol) in the presence of an oxidant capable of converting HBr to Br2.287 Gerasimov prepared 4-

Scheme 86

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methane.296 Nedolya et al. prepared 2,2-bis(3,5-dibromo-4hydroxyphenyl)propane by bromination of 2,2-bis(4-hydroxyphenyl)propane with bromine in dichloromethane using a mixture of water and 30% aqueous hydrogen peroxide.297 Similarly, oxidative bromination of the 2,2-bis(4′-hydroxyphenyl)propane using bromine and hydrogen peroxide can selectively produce the dibromo or tetrabromo derivative depending on the solvent and the reaction time.298 Choudary et al. reported in their paper an integrated approach of bromination coupled with oxybromination of aromatic compounds.299 They aimed at the utilization of both bromine atoms of the bromine molecule. They exemplified the method for bromination of bisphenol A using layered double hydroxide (LDH)−WO4 as a catalyst in the presence of aqueous H2O2 as an oxidant in a biphase comprising dichloroethane and water to produce tetrabromobisphenol A in high yield (Scheme 91).

bromo-1-(methylamino)anthraquinone by treating a suspension of 1-(methylamino)anthraquinone in methanol or aqueous methanol with bromine and aqueous hydrogen peroxide.288 Bromination of O-acyl esters of 1,4-benzoquinone mono- and -dioximes gave the unstable 5,6-dibromo- and 2,5,6-tribromo-2cyclohexene-1,4-dione mono-O-aroyl oximes, which underwent dehydrohalogenation to the corresponding 2-bromo- and 2,6dibromobenzoquinone mono- and dioximes.289 When 1,5dimethylnaphthalene was treated with bromine in CCl4 containing Fe powder, the reaction produced a mixture of 2-, 3-, and 4-bromo- and 2,6-, 2,7-, and 3,7-dibromo-1,5dimethylnaphthalenes. The extent of bromination and the product ratio are dependent on the reaction conditions and the amount of catalyst, respectively. It was observed that decreasing the amount of catalyst increases the proportion of 2-bromoand 2,6-dibromo-1,5-dimethylnaphthalenes.290 Zhu et al. carried out regioselective bromination of apogossypol hexamethyl ether.291 They found that bromination under different conditions produces different bromo adducts. For example, the use of Br2 in CCl4 with ultrasound irradiation produces the corresponding tetrabrominated product in high yield (Scheme 89). However, treatment of the same compound with bromine and Fe powder in CCl4 at −5 °C produces the tribrominated product exclusively.

Scheme 91

Zhang et al. described an improved procedure for aerobic oxybromination of bisphenol A to the corresponding tetrabromobisphenol A utilizing a combination of molecular bromine and molecular oxygen in the presence of sodium nitrite as the catalyst.300 The flame-retardant tetrabromobisphenol A bis(2,3-dibromopropyl) ether was synthesized from tetrabromobisphenol A diallyl ether by bromination with bromine.301 In the preparation of 3-phenylpyruvamine 2oximes as antifouling agents, Proksch et al. used Br2/DMC/ Et2O-mediated bromination of bisphenol.302 Zeolites were also used as catalysts in such bromination reactions.303−305 Bromination of aromatic substrates, namely, toluene, phenol, phenyl acetate, and chlorobenzene, resulted in the predominant formation of p-bromo derivatives (Scheme 92). The zeolitemediated bromination proceeds very smoothly, reflecting the catalytic activity of zeolite in this reaction.

Scheme 89

In the presence of silica, a number of aromatic hydrocarbons, such as toluene, o-, m-, and p-xylene, anthracene, and phenol, were brominated by bromine under mild conditions by Ghiaci et al.292 For example, Br2/SiO2 brominates naphthalene readily at 25 °C to produce 1- bromonaphthalene. 2,7-Dibromopyrene was prepared by bromination of 4,5,9,10-tetrahydropyrene with bromine in an aqueous medium in the presence of FeCl3 as the catalyst, followed by dehydrogenation with bromine in CS2.293 In this process, initially, 4,5,9,10-tetrahydropyrene was brominated to produce 2,7-dibromo-4,5,9,10-tetrahydropyrene, which was further subjected to dehydrogenation to produce the desired compound (Scheme 90).

Scheme 92

Scheme 90

Wortel et al. reported that the bromination of halobenzenes using bromine can be achieved at 25 °C in the presence of cation-exchanged Y-zeolites as catalysts.306 They reported that the catalyst activity and para/ortho ratio depend upon the type of cation, the extent of cation exchange, the activation temperature, the solvent, and the amount of catalyst used. It was found that in all cases the para/ortho ratio was considerably higher than that with conventional procedures. A similar method of synthesis of p-dibromobenzene by oxidative bromination of benzene with bromine in the gas phase in the presence of a zeolite-supported Cu catalyst has been reported by Ishida.307 A selective brominating system, Br2/SO2Cl2/zeolite, was discovered by Gnaim et al. for regioselective bromination of aromatic compounds.308 Partially cation-exchanged Ca2+-Y-zeolite efficiently catalyzes the

The bromination of dimethyl[2.2]metacyclophanene with Br2 in CCl4 solution at room temperature for 10 min afforded tetrabromodihydropyrene in 79% yield. However, a similar reaction of the dichloro derivative at room temperature for 2 h gave dibromodihydropyrene in 25% yield.294 Bromination of 4p-toluenesulfonamidobiphenyl was studied by Bell using bromine. He found that the use of pyridine as the solvent gave the 3,5-dibromo derivative, whereas the reaction in chloroform produced the 3,4′-dibromo derivative. The 3,4′derivative and bromine in pyridine gave quantitatively the 3,5,4′-tribromine derivative.295 Waters studied some substitution reactions of 4-aminodiphenylmethane using bromine in cold acetic acid to synthesize 3,5-dibromo-4-aminodiphenyl6855


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dichloromethane, tetrachloroethane, or chlorobenzene in the presence of AlCl3, FeCl3, or ZnCl2 (Scheme 95).319

selective para bromination of neat chlorobenzene by Br2/ SO2Cl2, affording a chlorobenzene conversion of 89% and a para selectivity of 97% (Scheme 93). During the bromination

Scheme 95

Scheme 93

reaction, SO2Cl2 oxidizes HBr, prevents its accumulation within the zeolite pores, and yields a more active brominating species. The system can brominate other activated aromatic compounds such as o-xylene, toluene, and fluorobenzene. Bauer and Enres reported some findings on the action of bromine on fatty aromatic compounds.309 They reported that 4-benzylbenzoic acid with an excess of bromine at room temperature produced tribromo-p-benzylbenzoic acid (Scheme 94). However, the reaction in a sealed tube at 110−120 °C for

Treatment of 1,2-bis(2-phenoxypropan-2-yl)diazene with bromine in a molar ratio of 1:2 produced 68% o-bromophenol and 2% p-bromophenol, whereas with a reactant ratio of 1:7, 88% p-bromophenol was isolated exclusively (Scheme 96).320 Scheme 96

Scheme 94

Partial bromination on noncondensed ring aromatics was achieved by adding the aromatic substrate to molecular bromine containing a zirconium halide catalyst at 30 °C.321A procedure for the preparation of 4-bromoisophthalic acid was developed by Feld. In this case, m-xylene in acetic acid was treated with bromine, and the solution thereby obtained was oxidized in the next step with oxygen.322 In the preparation of C1-6-alkylenebis(tetrabromophthalimide)s, N,N′-ethylenediphthalimide was brominated with bromine in fuming sulfuric acid to give 96% N,N′-ethylenebis(tetrabromophthalimide).323 A similar process for the preparation of N,N′-ethylenebis(tetrabromophthalimide) was reported by Wang.324 The reaction was carried out via condensation of phthalic anhydride with ethylenediamine in water at high temperature, followed by bromination with bromine in sulfuric acid in the presence of FeCl3 (Scheme 97).

4 h produced dibromotetraphenylethylenedicarboxylic acid. αPhenylphthalide did not react with bromine at room temperature but in sealed tubes at 120 °C for several hours yielded the dihydroxytetraphenylethanecarboxylic dilactone. Heller et al. studied the action of bromine on acetamidohydroxybenzoic acids and acetamidophenols. For example, 5acetamido-2-hydroxybenzoic acid with 3 mol of bromine without or with heating on a water bath produced the monobromine derivative.310 Bromination of dialkoxybenzaldehydes or -benzoic acids with bromine yielded large quantities of the 5-bromo derivatives and small amounts of the dibromo derivatives of the resorcinol dialkyl ethers.311 Jadhav and coworkers carried out bromination of phenyl and tolyl esters of m- and p-nitrobenzoic acids by heating the unsubstituted esters with bromine to produce 4-bromo, 4,5-dibromo, and 3,5,6tribromo products.312 Similarly, the isomeric tolyl benzoates and the corresponding nitrophenyl benzoates were brominated with bromine in the presence of fuming nitric acid as the catalyst.313 Bromination of 1-hydroxy-2-naphthoylanilide with 1 mol of bromine in chloroform gives 4-bromo-1-hydroxy-2naphthanilide, which could be further brominated in acetic acid to give 4-bromo-1-hydroxy-2-naphtho-p-bromoanilide. By similar methods, some analogous compounds were also prepared.314 Pajeau used Be and bromine in diethyl ether for bromination of different aromatic compounds.315In the synthesis of 3,5-dibromosulfanilanilide and its derivatives, bromine in acetic acid was used for bromination.3162,4-Dibromonaphthostyril-N-acetic acids were prepared from naphthostyril-Nacetic acid by aqueous bromination with bromine at 45 °C or H2SO4−HNO3 and a bromide salt at 60 °C.317 Perbromoaromatic compounds such as perbromobenzene, 2,3,4,5,6pentabromophenol, etc. were prepared by refluxing the corresponding aromatics in bromine containing AlBr3.318 3(4-Bromophenoxy)benzaldehyde was prepared in 81−87% yield by brominating 3-phenoxybenzaldehyde by bromine in

Scheme 97

Regioselective halogenation of tris(arylamido)phosphazobenzenes with bromine was reported by Kostina et al., affording the entirely para-substituted product.325 In the case of bromination, intermediate phosphonium bromide (p-BrC6H4)4P+Br− was isolated in quantitative yield. Ransford reported the synthesis of decabromodiphenylalkane by AlCl3-catalyzed bromination of diphenylalkane with bromine. Thus, for 1,2-diphenylethane, bromination with bromine in the presence of AlCl3 produced a 95% yield of 1,2-bis(perbromophenyl)ethane after workup under alkaline conditions (Scheme 98).326 6856


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Scheme 98

Scheme 100

Bromo-4-R-4′-chloro-2′-nitrodiphenyl ethers were prepared by bromination of 4-R-4′-chloro-2′- nitrodiphenyl ethers with bromine in carbon tetrachloride in the presence of Fe/I2 at 80 °C for 6 h.335 Multibromination of chloro-substituted nitrodiphenyl ether was studied by Wang et al.336 For example, refluxing 4-chloro-2-nitrophenyl ether with bromine in carbon tetrachloride in the presence of Fe and iodine for 8 h produced 61% 4-chloro-2-nitrophenyl 2,4-dibromophenyl ether. The bromination of nitrotriphenyl ether was studied, and six new bromo-substituted nitrotriphenyl ethers were synthesized.337 For example, bromination of 1,4-bis(4-nitrophenoxy)benzene with bromine in carbon tetrachloride in the presence of Fe and iodine at 80 °C for 1 h produced 2-bromo-1,4-bis(4nitrophenoxy)benzene in 72% yield (Scheme 101).

McKinnie et al. developed a process for bromination of noncondensed aromatic compounds.327 The reaction was done by adding a stoichiometric amount of bromine to a mixture comprising a noncondensed ring polyaromatic, a solvent such as dibromomethane or dichloromethane, and a catalyst such as ZrCl4, iron, or ferric chloride. The reaction mass was maintained at a temperature within the range from about 10 °C to about 50 °C during the time bromine was being added. Yamato et al. reported a method for bromination of cyclophanes using bromine.328 They disclosed that 9,17dimethyl[3.2]metacyclophane with 6 mol equiv of bromine in carbon tetrachloride produced bromobis(bromomethyl)cyclophane. However, treating the same compound with Br2/Fe powder in carbon tetrachloride produced dibromodimethylcyclophane. The bromination of 6,14-di-tert-butyl-9,17-dimethyl[3.2]metacyclophane produced the bromobis(bromomethyl) and dibromobis(bromomethyl) derivatives. Again the polybromination of the [2.2]paracyclophane compound with excess bromine was carried out by Nikanorov.329 The reaction was carried out in carbon tetrachloride without a catalyst to produce a reaction mixture containing equimolar amounts of 4,15- and 4,16-dibromo[2.2]paracyclophanes along with two other aromatic tribromides, 4,12,15- and 4,15,16-tribromo[2.2]paracyclophanes. When 1,4-dimethoxybenzene in acetic acid was treated with a solution of bromine (2 mol equiv) in acetic acid at room temperature, the corresponding 2,5-dibromo-1,4dimethoxybenzene was isolated after 2 h of reaction.330The resulting product was further oxidized with ceric ammonium nitrate in acetonitrile to produce 2,5-dibromobenzoquinone. However, when 2,5-dimethoxybenzaldehyde was subjected to bromination with bromine in glacial acetic acid, an 87% yield of 4-bromo-2,5-dimethoxybenzaldehyde was produced along with a 5% yield of 6-bromo-2,5-dimethoxybenzaldehyde (Scheme 99).331

Scheme 101

Yoshikawa disclosed a method for producing a dibromofluorobenzene derivative by bromination with a bromine.338 For example, bromination of 5-bromo-1,2-diethoxy-3-fluorobenzene with bromine in the presence of a mixture of sodium acetate and acetic acid produced 1,2-dibromo-4,5-diethoxy-3fluorobenzene in 100% yield (Scheme 102). Scheme 102

Scheme 99

Bromination of 5,6-disubstituted indane-1-one can be carried out using bromine under acidic and basic conditions.339 Bromination of 5,6-dimethoxyindan-1-one with bromine in acetic acid at room temperature produced exclusively the corresponding 2,4-dibromo compound in 95% yield (Scheme 103). Reaction of the same compound with bromine in the

4-Bromo-3-alkylphenyl ethers were prepared by bromination of 3-alkylphenyl ethers in the gas phase. Thus, 3-methylanisole vapor was heated with bromine vapor, which produced a 96% yield of 4-bromo-3-methylanisole.332 Akhrem et al. described a method for the synthesis of decabromodiphenyl ether by bromination of diphenyl ether with 11−14 mol equiv of bromine and 0.1−0.15 mol equiv of AlBr3 catalyst.333 The reaction was conducted for 2.5 h at room temperature. 4Bromophenyl alkyl ethers were prepared by reaction of alkoxybenzene with bromine in acetic acid in the presence of an oxidant capable of oxidizing HBr to bromine.334 Thus, ethoxybenzene in acetic acid was treated with 35% hydrogen peroxide and then with bromine at 30−35 °C to produce 4bromoethoxybenzene in 90% yield (Scheme 100).

Scheme 103

presence of KOH, K2CO3, or CS2CO3 at 0 °C gave the monobrominated product 4-bromo-5,6-dimethoxyindan-3-one in 79%, 81%, and 67% yields, respectively (Scheme 104). On the other hand, 5,6-dihydroxyindan-1-one undergoes dibromination on the aromatic ring, affording 4,7-dibromo-5,6dihydroxyindan-1-one both in acetic acid at room temperature and in the presence of KOH at 0 °C. However, the selectivity in 6857


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methoxy-2-hydroxyacetophenone was obtained in 44.5% yield (Scheme 108).

Scheme 104

Scheme 108 the case of 5,6-difluoroindan-1-one and 1-indanone was found to be reversed, where α-monobromination was observed in acetic acid and α,α-dibromination occurred under the influence of KOH at room temperature. Bromination of 2-acetyl-7-(methylamino)tropone with bromine in methanol produces 2-acetyl-4-bromo-7-(methylamino) tropone in 70% yield, which when treated with sodium hydroxide in methanol produces 3-acetyl-5-bromotropolone in 63% yield (Scheme 105).340

Park et al. used tetrabutylammonium peroxydisulfate in the bromination of aromatic compounds with bromine. Direct bromination of a wide range of aromatic compounds substituted with electron-donating groups such as methoxy, hydroxy, or amino groups has been achieved with high regioselectivity by the reaction with bromine in the presence of tetrabutylammonium peroxydisulfate under mild conditions in acetonitrile in excellent yields (Scheme 109).346

Scheme 105

Scheme 109 A method for the preparation of monoazidodibromodimethylmononitrobenzene was developed by Venkat, where the bromination in the intermediate step of the synthesis was carried out by using bromine at 0 °C.341 Andrievskii carried out bromination reactions of substituted 2,4-dinitrobenzene, 2,4,7trinitro-9-fluorenone, 2,4,8-trinitro-5H-phenanthridin-6-one, and 1,5-dinitro-9,10-anthraquinone with bromine−nitric acid in sulfuric acid or oleum to produce 83−97% substituted 2bromo-4,6-dinitrobenzene (Scheme 106), 96% 5-bromo-2,4,7trinitro-9-fluorenone, 82% 10-bromo-2,4,8-trinitro-5H-phenanthridin-6-one, and 3,4,7,8-tetrabromo-1,5-dinitro-9,10-anthraquinone, respectively.342

Bromination of aromatic compounds has been reported using hexamethylenetetramine and bromine in dichloromethane.347 This is an efficient regioselective method for bromination of aromatic compounds. The selectivity depends on the temperature and nature of the substituent on the substrate. The reactivity of this reagent was increased by supporting it on silica gel for bromination of less activated compounds (Scheme 110).

Scheme 106

Scheme 110

The production of 2,6-dibromoaniline was achieved by neutralizing 4-aminobenzenesulfonic acid with a base in water, brominating with bromine at 0−5 °C to obtain 4-amino-3,5dibromobenzenesulfonate, and desulfonating with 40−80% sulfuric acid at 120−170 °C for 1−6 h.348 Wang et al. used bromine for bromination of 4-methylaniline in the synthesis of 4-bromo-3,5-dimethoxybenzaldehyde.349 The compound 3,5dibromo-4-hydroxybenzonitrile was prepared from p-hydroxybenzaldehyde by reaction with hydroxylamine hydrochloride in DMF, dehydration, and bromination with Br2/H2O2.350 Bromination under alkaline conditions has been utilized as the key step for the synthesis of 3,4,9,10-tetrakis(disubstituted amino)perylenes from 3,4,9,10-tetracarboxyperylene.351 A method for the preparation of bromofluorenes (e.g., 2,7dibromofluorene) was disclosed by Hachiya et al, where the bromination was initiated by adding bromine into the disperse system.352 Brominated formylhydroxybenzophenones were prepared as intermediates in the synthesis of spirobenzopyranindolines.353 The process involves the treatment of 4hydroxybenzophenone with chloroform in aqueous sodium hydroxide to afford 3-formyl-4-hydroxybenzophenone. Neutralization of the reaction mixture with 10% sulfuric acid and

Cardanol, when treated with 2 equiv of bromine in carbon tetrachloride, underwent tetrabromination of the side chain, with subsequent bromination occurring on the aromatic ring.343 6-tert-Butylcardanol was also subjected to bromination, and the effects of acetic acid and sulfuric acid (in place of carbon tetrachloride) at room temperature were examined. Bromination of acetophenone with bromine in the presence of AlCl3 produced 82% 3-bromoacetophenone (Scheme 107), which was refluxed with phenol in xylene in the presence of KOH and Cu(OAc)2 to give 93% 3-phenoxyacetophenone.344 The bromination of paeonol with bromine was studied by Qi et al.345 When paeonol was brominated with bromine in anhydrous diethyl ether and anhydrous AlCl3, 5-bromo-4Scheme 107

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followed by cooling to 10−40 °C, and then bromine diluted by HBr was dripped at 45−65 °C for 1−3 h.362 Jian et al. reported a procedure for the preparation of 2,6-dibromo-4-nitroaniline diazonium salt from p-nitroaniline. Here they added bromine as one of the brominating agents.363 p-Bromotoluene and obromotoluene were synthesized by a one-pot reaction using water as the solvent and toluene, 1-propanol, and bromine as substrates. Meanwhile, the hydrogen bromide, generated during bromination of toluene, was used to synthesize 1-bromopropane. The yields of p-bromotoluene and o-bromotoluene were 66.4% and 24.7%, respectively. The yield of 1-bromopropane was up to 80% after refluxing for 1.5 h in 1-propanol.364 2Methyl-4-bromophenoxyacetate was obtained via the AlCl3- or HgCl2-catalyzed bromination of 2-methylphenoxyacetic acid with bromine in glacial acetic acid followed by the reaction of 2methyl-4-bromophenoxyacetic acid with triethanolamine.365 Zhao and co-workers reported a multistep process for the synthesis of pinaverium bromide. In one of the steps, 3,4dimethoxybenzyl alcohol and bromine were reacted in the presence acetic acid to obtain 2-bromo-4,5-dimethoxybenzyl bromide (Scheme 113).366

bromination with bromine produced 5-bromo-3-formyl-2hydroxybenzophenone. A pesticide intermediate, 3-bromobenzaldehyde, was synthesized from benzaldehyde and bromine in the presence of anhydrous AlCl3 by Zhao et al.354 in 1,2dichloroethane at 40−45 °C (Scheme 111). The optimum ratio of benzaldehyde and AlCl3 was found to be 1:1.3 to obtain a maximum yield of 91.8% of the corresponding brominated product. Scheme 111

The compound 6,6′-dibromo-2,2′-bis(hexyloxy)-1,1′-binaphthalene was prepared in 94.7% yield by bromination of 2,2′binaphthol with bromine followed by alkylation with hexyl bromide for 3 h at reflux temperature to produce 41.3% methyl 4-morpholin-4-yl-5-p-tolyl-1(2)H-pyrazole-3-carboxylate.355 In the intermediate step of the preparation of halofuginone hydrobromide, bromine was used for bromination of 3chlorotoluene in the presence of FeCl3 to obtain 2,4dibromo-5-chlorotoluene356 Wang et al. prepared 3,5-dibromo-2(or 4)-hydroxyphenyl 4-fluorophenyl ether by refluxing 2(or 4)-hydroxyphenyl 4-fluorophenyl ether with bromine in a mixture of dichloromethane and ethyl acetate.357 Jiang described a synthetic procedure for the preparation of [1,1′biphenyl]-2,5-dicarboxylic acid.358 Here, p-xylene reacts with bromine in the presence of iron filings at room temperature to provide 2-bromo-p-xylene. Further reaction of this product in a copper-assisted coupling reaction with bromobenzene in the presence of NiCl2(PPh3)2 provided 2,5-dimethylbiphenyl. Then 2,5-dimethyl-1,1′-biphenyl was oxidized with KMnO4 to give the final product. The heterogeneous kinetics of the catalytic bromination of anthracene on silica gel was investigated by Seetula.359 The surface of the silica gel was treated with bromine in carbon tetrachloride for their investigation. Anthracene was brominated catalytically to produce 9bromoanthracene as the only aromatic product of the reaction. Bromination of 9-bromoanthracene using Br2/silica could produce 9,10-dibromoanthracene as the final product. Further bromination of 9,10-dibromoanthracene could not be achieved under this condition. A method for the synthesis of 4-bromoN,N-dimethylaniline was reported by Shi et al.360 In the presence of pyridine, it was synthesized via a substitution reaction starting from N,N-dimethylaniline and bromine (Scheme 112).

Scheme 113

A process for the preparation of 1,5-naphthalenediamine via the selective halogenation of 1-nitronaphthalene was disclosed by Bergner et al.367 For example, FeCl2-mediated regioselective bromination of 1-nitronaphthalene using bromine in chloroform afforded 1-nitro-5-bromonaphthalene in 77% yield. Then 1-nitro-5-bromonaphthaline was converted to 1,5-naphthalendiamine in two steps. In the synthesis of brodimoprim, 3,5dihydroxybenzoic acid was brominated with bromine at 107− 108 °C for 3 h. It was then methylated with dimethyl sulfate, chlorinated with thionyl chloride, and reduced with hydrogen in xylene in the presence of Pd/BaSO4 at 114 °C. The resulting compound was condensed with acrylonitrile in methanol in the presence of sodium methoxide and cyclized with guanidine nitrate to give the final product.368 The (2,6-diisopropyl-4phenoxyphenyl)thiourea was prepared by Yu et al. Here, the first step of the process is the synthesis of a key intermediate of diafenthiuron by brominating 2,6-diisopropylaniline with bromine in toluene or xylene at subzero temperature (75%). 3.2.2.64. 1,2-Dipyridinium Ditribromide−Ethane.

1,2-Dipyridinium ditribromide−ethane (DPTBE) was synthesized and explored as a new efficient brominating agent by Kavala et al.1147 It is a crystalline ditribromide reagent, and 0.5 equiv of the reagent was required for complete bromination. The reactions were very simple and were conducted by just grinding the reagent and substrates in a porcelain mortar at room temperature without using any solvent. The products were easily isolated by just washing the highly water-soluble DPDBE from the brominated product. The spent reagent could be recovered, regenerated, and reused without any significant loss. They applied this reagent to acetanilides, phenols, and anilines to give the p-bromo products. Phenolic substrates bearing benzyloxy, carbonyl, and benzoyl groups gave the corresponding o-bromo products. The fused ring phenolic compound α-naphthol afforded the expected 2-bromo-αnaphthol. This reagent also brominated several other functionalities, such as ethylenic, acetylinic, and carbonyl, efficiently (Scheme 394). The α-bromination reaction of arylacenones with DPTBE as the brominating agent under solvent-free conditions selectively gave the corresponding α-bromoarylacenone derivative in excellent yields.1148

Amer et al. investigated a number of N-substituted aminotriphenylphosphonium tribromides to test their bromination ability of the phenols.1150 They showed that (tert-butylamino) triphenylphosphonium tribromide is a very good and highly regiospecific brominating agent. They examined the efficacy of the reagent for the bromination of several substituted phenols in a mixture of dichloromethane and methanol at room temperature to produce the monobrominated product. 3.2.2.67. Bromodimethylsulfonium Bromide.

Bromodimethylsulfonium bromide (BDMS) exhibits a good brominating property. Several studies were undertaken using this reagent for organic transformations.1151−1153 BDMS can be prepared from liquid bromine and dimethyl sulfide.1154 6910


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Epoxides upon treatment with bromodimethylsulfonium bromides in the presence of triethylamine give α-bromo ketones in high yields (Scheme 396). The reaction proceeds

Scheme 399

Scheme 396 Treatment of Baylis−Hillman adducts with BDMS in MeCN was found to stereoselectively afford (Z)- and (E)-allyl bromides. The reaction is rapid at room temperature, highyielding, and highly stereoselective.1159 Poly(methylhydrosiloxane) (PMHS) in combination with BDMS or NBS was utilized for the first time for the reductive bromination of aromatic aldehydes at room temperature to afford the corresponding benzyl bromides in excellent yields.1160 Alkenes and alkynes were brominated efficiently in high yields with BDMS in acetonitrile at room temperature. Alkenes produced the corresponding trans-dibromo compounds, while alkynes (except phenylacetylene) afforded both the trans-dibromo products (major) and the tetrabromo derivatives (minor). However, phenylacetylene furnished solely the tetrabromo compound.1161 Khan et al. carried out regioselective ring monobromination of a wide variety of (E)-1-(2′-hydroxy-4′,6′dimethoxyphenyl)-3-aryl-2-propen-1-ones using 1.5 equiv of BDMS at room temperature (Scheme 400).1162 When the reaction was carried out usng 4 equiv of BDMS, vicinal dibromination along with monobromination of the aromatic ring was observed.

well with alkene oxides and cycloalkene oxides of small ring sizes. Epoxides with medium and large ring sizes undergo transannular rearrangements, giving mixtures of products. Similarly, enamines react with BDMS to give α-bromo ketones.1155 This reagent also acts as an efficient regioselective brominating agent for activated aromatics such as phenols, anisole, diphenyl ether, and N-alkylanilines. Chow et al. observed high para selectivity in all cases. A typical feature of this method is that para-substituted aromatics do not undergo further bromination reaction (Scheme 397).1156 Scheme 397

Scheme 400

Majetich et al. used BDMS, generated in situ, by treating dimethyl sulfoxide with aqueous hydrobromic acid as a milder and more selective reagent for electrophilic aromatic bromination (Scheme 398).1157 A variety of substrates were

3.2.2.68. Chiral Brominating Agents. Duhamel synthesized some chiral brominating agents, which were chiral N-bromo carbamates, amides, and imides and N-bromooxazolidinones.1163 Acetyl hypobromite and tert-butyl hypochlorite are the reagents of choice to synthesize these compounds. These reagents led to enantiomeric halogenations. The brominating agents are shown in Figure 2.

Scheme 398

Figure 2. Chiral brominating agents.

brominated. They established two general protocols for aromatic bromination with BDMS generated in situ. The addition of aqueous hydrobromic acid to a solution of the substrate in DMSO was one procedure, and in another general procedure the DMSO was added to a solution of the substrate in acetic acid and aqueous hydrobromic acid. Six aryl methyl ethers were brominated by using these general procedures. Each of these examples produced the monobromides free of side products. Khan et al. reported this compound as an effective and regioselective reagent for α-monobromination of β-keto esters and 1,3-diketones. A wide variety of β-keto esters and 1,3diketones undergo chemoselective α-monobromination with excellent yields at 0−5 °C or room temperature (Scheme 399).1158

3.2.2.69. Ethylenebis(N-methylimidazolium) Ditribromide. A regioselective and highly efficient method for the bromination of phenol and aniline derivatives using ethylenebis(N-methylimidazolium) ditribromide (EBMIDTB) as an efficient reagent in dichloromethane at ambient temperature was reported by Hosseinzadeh and co-workers (Scheme 401).1164 EBMIDTB is easily and cheaply prepared from Nmethylimidazole, 1,2- dibromoethane, and bromine. The reaction conditions were very simple. The same group reported the monobromination of 1,3diketones and β-keto esters using this reagent. 1,3-Diketones and β-keto esters were brominated chemoselectively to the corresponding α-monobrominated products at 0−5 °C. Under the same reaction conditions, diethylmalonate, ethyl cyanoace6911


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Scheme 401

group were more reactive than aromatic aldehydes with an electron-withdrawing group and aliphatic aldehydes.1169Kim et al. established the optimal conditions for the Wittig reaction for synthesizing α-bromoacrylates with a high selectivity, and developed a simple and efficient one-pot procedure for preparing various conjugated acetylenic carboxylates in moderate to high yields (Scheme 404).1170

tate, and malononitrile were monobrominated in moderate yield.1165 3.2.2.70. Hexabromoacetone.

Scheme 404

Bromosilanes were prepared conveniently and efficiently via the reaction of hydrosilanes and Br3CCOOEt in the presence of a catalytic amount of PdCl2.1171 The reactions were carried out by taking hydrosilanes in refluxing THF over 15 min in high yields (Scheme 405).

Hexabromoacetone can be used for the synthesis of acyl bromide from carboxylic acid.1166 Primary alcohols, when treated with (Br3C)2CO in DMF at 60 °C, the produce the corresponding alkyl 2,2,2-tribromoacetates in high yield.1167 Similarly, primary amides can be converted into the corresponding 2,2,2-tribromo-N-alkylacetamides by carrying out the reaction in chloroform at room temperature. Furthermore, the reagent can act as a brominating agent, in the presence of triphenylphosphine, in the conversion of benzoic acids into the respective amines (Scheme 402).

Scheme 405

3.2.2.72. Pentylpyridinium Tribromide.

Scheme 402 A room temperature ionic liquid, pentylpyridinium tribromide, was synthesized and characterized by Salazar et al., and this reagent was used as a vapor-pressure-free bromine analogue for the bromination of ketones, aromatics, alkenes, and alkynes.1172 The brominations were carried out in the absence of organic solvents, and in most cases the only solvent needed for extraction was water. Ketones were cleanly and selectively monobrominated without the formation of side products. Aromatic compounds were brominated with complete selectivity. For example, phenol was cleanly monobrominated in the absence of a solvent at room temperature. Treatment of alkenes and alkynes with this reagent results in the formation of the corresponding dibrominated products (Scheme 406).

3.2.2.71. Ethyl Tribromoacetate.

Scheme 406 Acid bromides were prepared efficiently from carboxylic acids with readily available ethyl tribromoacetate and triphenylphosphine at room temperature under neutral conditions.1168 This process was applicable for the preparation of various amides from aromatic and aliphatic carboxylic acids (Scheme 403). Aromatic carboxylic acids were found to be more reactive than aliphatic carboxylic acids under the reaction conditions. Scheme 403

3.2.2.73. 3-Bromo-4,4-dimethyl-2-oxazolidinone. A method of preparing acid bromides directly from aldehydes with Br3CCO2Et under radical conditions was developed by Kang et al. In this method a mixture of aldehyde and Br3CCO2Et in chlorobenzene under argon was heated to 110 °C for 24 h. During the reflux, benzoyl peroxide was added. They found that aromatic aldehydes with an electron-donating

3-Bromo-4,4-dimethyl-2-oxazolidinone (NBDMO) was prepared by Kaminski and co-workers, and its reactions were compared to those of N-bromosuccinimide (NBS).1173They determined the “bromine potential” in terms of the equilibrium 6912


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reactions were carried out using CetPyTB in acetonitrile at room temperature (Scheme 409). Various organic substrates

constant for the reversible reaction between 3-bromo-4,4dimethyl-2-oxazolidinone and succinimide to form 4,4dimethyl-2-oxazolidinone and N-bromosuccinimide. They found that it had a less polar N-bromine bond. Next they investigated the behavior of NBDMO in several reactions characteristic for NBS, such as oxidation of secondary alcohol and allylic bromination. For allylic bromination, the transformation of cholesteryl benzoate to 7-dehydrocholesteryl benzoate was investigated. In this instance, the 7-bromocholesteryl benzoate intermediate was dehydrobrominated in situ to give 7-dehydrocholesteryl benzoate. NBDMO was found to be equivalent to or better than NBS as a brominating agent in the reactions investigated. 3.2.2.74. 4,4-Dibromo-3-methylpyrazol-5-one.

Scheme 409

such as phenols, anilines, anthracene, chalcone, etc were brominated efficiently with this reagent. They also reported the catalytic property of this reagent in the acetylation reaction. 3.2.2.76. N,N,N′,N′-Tetrabromobenzene-1,3-disulfonamide. N,N,N′,N′-Tetrabromobenzene-1,3-disulfonamide

4,4-Dibromo-3-methylpyrazol-5-one was first established as a brominating agent by Mashraquf et al.1174 It was used for the selective para bromination of phenols and anilines under mild conditions. The bromination reaction was carried out by taking the substrates in glacial acetic acid at room temperature. Bromination of the para-substituted phenols produced the corresponding o-bromophenols, whereas o- and m-cresols predominantly exhibited para-selective bromination. Brominations of phenolic aldehyde and eugenol also led to the corresponding nuclear bromination products in high yield. Bromination of highly reactive aniline and N,N-dimethylaniline with this reagent afforded 90% para bromination accompanied by small amounts of the unreacted anilines and polybromo products. Acetanilide and benzanilide were cleanly brominated to produce the corresponding p-bromo products in excellent yields (Scheme 407).

(TBBDA) can be used for the regioselective bromination of aromatic compounds.1176 The reactions were carried out in dichloromethane with an excellent yield (Scheme 410). They also prepared a poly(N-bromobenzene-1,3-disulfonamide) as a heterogeneous reagent for the bromination of aromatic compounds in excellent yields. Scheme 410

TBBDA, poly(N,N/-dibromo-N-ethyl-benzene-1,3- disulfonamide) [PBBS], and poly(N,N/-dibromo-N-phenylbenzene1,3-disulfonamide) [PBPS] can be used for the bromination of benzylic positions in a solvent under reflux conditions in the presence of benzoyl peroxide.1177 CCl4 and EtOAc are the best solvents to carry out the bromination with these reagents (Scheme 411).

Scheme 407

Scheme 411

3.2.2.75. Cetylpyridinium Tribromide. 3.2.2.77. N-Bromophthalimide.

Kumar et al. proposed a new environmentally benign protocol for the synthesis of cetylpyridinium tribromide (CetPyTB).1175 This reagent can be prepared from cetylpyridinium bromide using KBr in the presence of V2O5 and H2O2 (Scheme 408). They showed that the reagent works efficiently as a brominating agent for electron-rich aromatic compounds. The

Reaction of substituted benzene rings with N-bromophthalimide (NBP), under neutral conditions, gave the corresponding bromo derivatives with a preference for the formation of the para isomer over the ortho isomer (Scheme 412).1178 NBP has also been used for the bromination of some deoxyhexoses.1179 Bromination of 1,5-anhydro-2-deoxy-D-arbino-hex-1-enitol in an aqueous solution at 0 °C with NBP produced a mixture of bromodeoxyhexoses from which 2-

Scheme 408

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nuclear bromination. The hydroxy aromatics and PBC were dissolved in the minimum amount of glacial acetic acid, and the reaction mixtures were heated with constant stirring. The time required for the reaction was 20−45 min. The synthesis of bromonitrophenols in good yields using the pyridinium bromochromate (PBC) reagent as the brominating agent was described by Gaspar et al.1184 The bromination reactions were performed using a higher brominating agent to substrate ratio. However, only the 2:1 molar ratio proved to be efficient; moreover, in most cases, only the dibrominated product was obtained. This reagent was also found to be a highly efficient and selective reagent for the α-monobromination of 1,3diketones and β-keto esters in the absence of a base, a Lewis acid, or another catalyst.1185 The products were formed in high to excellent yields under mild reaction conditions and in short reaction times. 3.2.2.80. Benzimidazolium Bromochromate.

Scheme 412

bromo-2-deoxy-D-mannose was isolated in 60% yield by crystallization. 3.2.2.78. Diethyl N,N-Dibromophosphoroamidate.

Ionic addition of diethyl N,N-dibromophosphoroamidate (DBPA) to alkenes and cycloalkenes was reported.1180 The addition of DBPA to a variety of phenylethylenes, straight-chain terminal and nonterminal alkenes, and cycloalkenes in the presence of boron trifluoride etherate was investigated. It was found that the reaction proceeds smoothly at −20 °C by adding an olefin to a solution of equimolar amounts of DBPA and boron trifluoride etherate in tetrachloromethane. N-Bromo adducts initially formed could be reduced in situ with sodium bisulfite solution to give the corresponding diethyl N-(βbromoalkyl)phosphoroamidates, which in turn afforded βbromo amine hydrochlorides upon treatment with hydrogen chloride in benzene at room temperature. The regiospecificity was typical for Markovnikov addition. The addition of DBPA to (E)-1-phenylpropene, (E)-2-butene, and (Z)-2-butene was also found to proceed stereospecifically, affording the corresponding anti adducts. 3.2.2.79. Pyridinium Bromochromate.

Ö zgün and Degirmenbaşi introduced benzimidazolium bromochromate (BIBC) for the bromination of various aromatic compounds.1186 This reagent was easily prepared from benzimidazole, 47% aqueous hydrobromic acid, and chromium(VI) oxide in a molar ratio of 1:1:1. The bromination reactions were carried out in an acetic acid solution of the reagent. They found that anisole, acetanilide, and benzanilide gave the 4-bromo derivatives. Fluorene gave 9-bromofluorene, and acetophenones were brominated in the ω-position (Scheme 414). Scheme 414

Pyridinium bromochromate (PBC) was synthesized by taking chromium trioxide in water and adding HBr with constant stirring. The contents were cooled to 0 °C, and then pyridine was added over 15−20 min to give the brown solid.1181 PBC was further used as a brominating agent for aromatic compounds. Thus, the addition of N-phenylbenzamide to the reagent in acetic acid produced 4-bromo-N-phenylbenzamide in 97% yield (Scheme 413).

3.2.2.81. Quinolinium Bromochromate.

Scheme 413 A new reagent, quinolinium bromochromate (QBC), functions as a good brominating agent for aromatic compounds. It was easily prepared from quinoline, 47% aqueous hydrobromic acid, and chromium(VI) oxide in a molar ratio of 1:1:1.1187 QBC is a mustard yellow, nonhygroscopic, air-stable, but moderately light sensitive solid which should be protected from light during preparation and storage. Anisole and acetanilide when heated at 90−100 °C with 2 equiv of QBC in acetic acid give the respective bromo derivatives in good yields (Scheme 415). It was also found that when the alcohol was added to a solution of QBC in CH2Cl2 and refluxed for 3−4 h, the reaction produced the corresponding ketones in high yield.

The photochemical and thermal bromination of metal βdiketonate complexes of Mn(II), Co(II), Cu(II), Zn(II), Cr(III), Mn(III), Fe(III), Co(III), Ce(IV), Th(IV), and UVIO2 by PBC in glacial acetic acid was carried out by Samath et al.1182 Under ambient conditions, the tris and tetrakis chelates underwent electrophilic γ-bromination, whereas the bis chelates decomposed, yielding bromo complexes by nucleophilic addition of bromine. Under photoirradiation, λ = 254 or 357 nm, all the complexes, except those of Cr(III), Ce(IV), and Th(IV), which underwent electrophilic γ-substitution, decomposed, forming bromo complexes. In 2003, Patwari et al. reported this reagent as an efficient brominating agent for the bromination of hydroxy aromatics.1183 PBC was used to brominate various substituted hydroxyacetophenones, hydroxy aldehydes, and hydroxyphenols for efficient and selective

Scheme 415

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The reagent QBC can also act as a brominating agent for the bromination of metal β-diketonates.1188 Reactions of copper(II), cobalt(II), nickel(II), chromium(III), cobalt(III), and manganese(III) β-diketones with quinolinium bromochromate (QBC) in glacial HOAc medium at room temperature produce electrophilic γ-substituted bromo products. 3.2.2.82. Pyridinium Dichlorobromate.

Scheme 418

side chain bromination. They also found that the reagent can be used as an oxidizing agent for all kinds of alcohols to produce the corresponding aldehydes and ketones in dichloromethane at room temperature. 3.2.2.84. Bromine Supported on Resin. Active aromatic compounds were brominated by using ion-exchange-resinsupported bromine as the brominating agent. The products were monobromo compounds where the bromine atom occupied the para position of the activating group. The yields were found to be very good. 1191 Bromination of 3methylanisole with ion-exchange-resin-supported bromine gave 89% 4-bromo-3-methylanisole.1192 3.2.2.85. Cross-Linked Poly(vinylpyridinium hydrobromide perbromide) Resins. This reagent was used to brominate a number of alkenes and ketones.1193 In most cases, the brominated products were obtained in excellent yields and could be separated from the polymeric byproduct by a simple filtration. The polymeric reagent could be fully regenerated after use without loss of activity. For the synthesis of the reagent, first cross-linked bead polymers containing vinylpyridine units were prepared by pearl copolymerization of monomer mixtures containing various percentages of 4vinylpyridine, styrene, and divinylbenzene. The polymers were functionalized by reaction with hydrogen bromide and bromine, and the resulting poly(vinylpyridinium hydrobromide perbromide) resins were used to brominate substrates. This reagent was stable for long periods of time. Dibromides and αbromo ketones are thus prepared in 55−100% yield at room temperature or in refluxing methanol and are readily separated from the polymer. Typical compounds prepared are dldibromostilbene, 1,2,7,8-tetrabromooctane, 2,3-dibromo-3-phenylpropanoic acid, and 1-bromoethyl phenyl ketone (Scheme 419).

Pyridinium dichlorobromate (PyHBrCl2) is an example of an iminium−trihalide complex introduced by Muathen.1189 The compound was prepared from pyridine and chlorine in the presence of aqueous hydrogen bromide (Scheme 416). It shows a remarkable reactivity toward aromatic compounds compared with other bromine complexes. It is also considered as a potential source for bromine chloride (BrCl). Scheme 416

Three general procedures have been used for aromatic bromination depending on the activity of the aromatic ring (Scheme 417). Polyalkylbenzenes such as durene and Scheme 417

mesitylene are smoothly brominated at room temperature in a few minutes. The bromination of less reactive hydrocarbons, e.g., benzene and toluene, can be promoted by Lewis acids such as FeCl3 in dichloromethane at room temperature, and the corresponding bromoarene was isolated in high yield. Moderately reactive aromatics, such as anisole and acetanilide, can also be readily brominated with the complex to give a mixture of o- and p-bromo derivatives. Activated aromatic compounds, e.g., phenols and anilines, are brominated very smoothly to give the corresponding polybromo derivatives in aqueous methanol. 3.2.2.83. Quinoxalinium Bromochromate.

Scheme 419

3.2.2.86. Pyridine and Quinoline Derivatives of Poly(methyl methacrylate), a Polymeric Brominating Agent. Akelah et al. first synthesized pyridine and quinoline derivatives of poly(methyl methacrylate) (PMMA).1194 Nucleophilic substitutions of 2-picolinyl- and 2-quinaldinyllithium onto the carbonyls of the ester moieties of PMMA followed by reduction was carried out for the functionalization of PMMA. Then complexation of the polymeric pyridine derivatives with bromine was conducted to give various types of polymeric brominating agents. The activities of these cross-linked reagents were investigated for direct brominations of carbonyl compounds, alkenes, and arenes (Scheme 420). The reactions were carried out using the polymeric agent in methylene dichloride at room temperature. Excellent yields of the

Quinoxalinium bromochromate (QxBC) is a mustard yellow, nonhygroscopic, air-stable, but moderately light-sensitive solid. It can be prepared from chromium trioxide in water by adding hydrobromic acid at 0 °C.1190 It can be used as a brominating agent for aromatic compounds. The reactions were carried out in the presence of acetic acid in a heated water bath. The completion of the reaction was evidenced from a change in the color of the contents to green. Selective monobrominations were achieved with this reagent. For example, N-phenylbenzamide can be converted to N-(4-bromophenyl)benzamide using this reagent (Scheme 418). It was reported that QxBC is more efficient in the bromination of aromatic compounds than 6915


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activity of this poly(NBS) reagent was examined for bromination reaction on model compounds 2,2′-(1,4-phenylene)bis(1,3-dioxane) and its alkyl- and hydroxy-substituted derivatives.1200 The reaction was carried out by reaction of 2,2′(1,4-phenylene)bis(5,5-dimethyl-1,3-dioxane) with poly(NBS) in CCl4. Poly(NBS) was also found to be a good heterogeneous oxidizing agent for the conversion of acetals into esters. 3.2.2.90. 2-Methyl-4-poly(styrylmethyl)thiazolium Hydrotribromide. Kessat et al. reported a simple method of preparing 2-methyl-4-poly(styrylmethyl)thiazolium hydrotribromide, and then it was used effectively in heterolytic and homolytic bromination reactions.1201 They used it to brominate various ketones, olefins, phenol, thiazole, acetanilide, and diethyl malonate under different mild conditions. The bromination of styrene and cyclohexene was found to be quick, easy, and total (Scheme 422). The reaction was carried out by treating

Scheme 420

brominated products were obtained. The polymeric byproduct could be simply converted back to the reagent without loss of activity. These reagents are very stable at room temperature. 3.2.2.87. Poly(N-Bromoacrylamide). George and Pillai introduced this reagent as a polymeric recyclable brominating agent.1195 Poly(N-bromoacrylamide) was conveniently prepared from commercially available polyacrylamide and was developed as a new insoluble polymeric oxidizing and brominating reagent for organic substrates. The reagent was used to brominate unsaturated and aromatic substrates in high yields. This reagent can be stored for months without any loss of activity, can be handled easily, and can be recycled for further use. The capacity and reaction efficiency of the polymeric reagent were found to be practically unchanged even after seven cycles of operation. Poly(N-bromoacrylamide) reacts with olefinic compounds to give the corresponding dibromo derivatives (Scheme 421) in 72−76% yield. The reactions were

Scheme 422

the substrate with the 2-methyl-4-poly(styrylmethyl)thiazolium hydrotribromide in DCM at room temperature. The reagent was found to be stable and simply regenerable without loss of activity after several reaction cycles. 3.2.2.91. Cross-Linked Poly(4-vinylpyridine−styrene)−Bromine Complexes. Cross-linked poly(styrene−4-vinylpyridine) beads, containing 40−43% pyridine rings, were transformed with bromine to provide three types of brominating agents by Johar et al. (Scheme 423).1202 Reaction in chloroform in the presence of excess bromine resulted in the formation of several complexes.

Scheme 421

carried out by using poly(N-bromoacrylamide) in chloroform at room temperature. Phenol on reaction with this polymeric brominating reagent afforded 2,4,6-tribromophenol in 60% yield. Toluene afforded benzyl bromide under these conditions. Poly(N-bromoacrylamide) was also used to oxidize alcohols to the corresponding carbonyl compounds in near-quantitative yields at room temperature. 3.2.2.88. Poly(vinylbenzyltriphenylphosphonium perbromide). Akelah et al. prepared poly(vinylbenzyltriphenylphosphonium perbromide) and used it as a brominating agent for various organic compounds.1196 The reagent was prepared by the chemical modification of cross-linked poly(p-(bromomethyl)styrene) with triphenylphosphine followed by treatment of the obtained polymeric salt with bromine. It could brominate carbonyl compounds containing an α-hydrogen and alkenes. This reagent was easy to use and could be regenarated without loss of the brominating activity.1197 3.2.2.89. Poly(N-bromosuccinimide). This reagent was manufactured by radical-copolymerizing N-tert-alkylmaleimide, heating the copolymer at 250−400 °C to form polymaleimide, and finally brominating the polymaleimide.1198 In particular, the isobutyl vinyl ether−maleimide copolymer cross-linked with divinylbenzene or 3,9-bis(isopropenyl)-2,4,8,10-tetraoxaspiro[5.5]undecane was brominated to synthesize the poly(NBS). It was an effective brominating agent for 2,2′-(1,4phenylene)-bis(1,3-dioxane) and its alkyl derivatives.1199 The

Scheme 423

They studied various reactions to convert different organic substances to the corresponding bromo derivatives. They have also examined the stereochemical outcome of the reactions. Bromination of 1-phenylcyclohexene with reagents I and III resulted in the formation of trans-l,2-dibromo-l-phenylcyclohexane and 3-bromo-2-phenylcyclohexene, respectively (Scheme 424). Bromination of norbornene with reagents I, II, and III resulted in the formation of seven products: 2-exo-bromonorbornane, 7-bromonortricyclane, 2-exo-3-endo-dibromonorbornane, 2-exo-7-anti-dibromonorbornane, 2-exo-5-endo-dibromo6916


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monobrominated product in good yields at ambient temperature.1205 3.2.2.94. Benzyltriphenylphosphonium Tribromide. Hajipour and co-workers found that benzyltriphenylphosphonium tribromide (BTPTB) can be used for controlled and selective bromination of phenols.1206 They found that the treatment of phenols with benzyltriphenylphosphonium tribromide in a mixture of dichloromethane and methanol in 2:1 ratio at room tempetarue produces mono-, di-, and tribrominated phenols with high selectivity and good yields. 3.2.2.95. Methyltriphenylphosphonium Tribromide. Cristiano et al. developed a heterogeneous brominating agent, methyltriphenylphosphonium tribromide, bound on the surface of polystyrene beads.1207 This reagent was made in a two-step process. Initially, a triphenylphosphene-functionalized polystyrene was treated with an excess amount of methyl bromide to form the corresponding phosphonium salt. This salt was further treated with molecular bromine in dichloromethane to obtain the polymer-supported methyltriphenylphosphonium tribromide. This reagent was used for the bromination of various unsaturated substrates in a regio- and stereoselective manner. 3.2.2.96. Tetrapropylammonium Nonabromide, Pr4NBr9. Riedel and co-workers recently discovered a new type of solid brominating agent, tetrapropylammonium nonabromide.1208 The reagent can effect the bromination of a variety of compounds such as olefins, ketones, and aromatic compounds to produce the corresponding products at room temperature within a very short time. Although the reactivity of this reagent is comparable to that of elemental bromine, it shows a better selectivity profile. For example, vicinal dibromo compounds could be made from the corresponding olefins with high anti selectivity using this reagent.

Scheme 424

vorbornane, 2-exo-5-exo-dibromonorbornane, and 2-exo-7-syndibromonorbornane. 3.2.2.92. Poly(diallyldimethylammonium tribromide). Hossein et al. reported the synthesis and applications of the polymeric tribromide reagent poly(diallyldimethylammonium tribromide) (PDADMATB).1203 For the preparation of this compound, poly(diallyldimethylammonium bromide) was treated with KBr, followed by oxidation of bromide to bromine with an aqueous solution of oxone (Scheme 425). Scheme 425

This supported tribromide was used in α-bromoacetalization of ketones, bromination of alkenes, and regioselective bromination of activated aromatic compounds (Scheme 426).

3.3. Reagents Other Than Bromo-Organic as Well as Naturally Occurring Bromo Compounds

3.3.1. HOBr. When HOBr was added to a H2SO4 solution of C6H6 in water, immediately PhBr was separated. Similarly, benzoic acid was converted to m-bromobenzoic acid in fairly strong HNO3 or H2SO4. This reactivity is in accord with the view that Br+ or (H2O)Br+ is present as a result of equilibrium (Scheme 427).1209

Scheme 426

Scheme 427

Malinski et al. studied the product composition for the bromination of PhP(O)R2 (R = Me, i-Pr) with HOBr in 6 M H2SO4. Both phosphine oxides are meta-directing, but for the dimethyl derivative, a significant contribution from ortho substitution was observed (15%); no substitution at the para position could be detected.1210 Again α-bromo ketones are prepared from olefins using Br− and BrO3− as a couple. Several α-bromo ketones were successfully prepared from a variety of olefins by this method.1211 3.3.2. Phosphorus Oxybromide.

Bromination of various electron-rich aromatic compounds was performed with PDADMATB at 25 °C to give monobrominated products with high regioselectivity. This method was mild, and the reagent was stable, highly efficient, and reusable. 3.2.2.93. Poly(vinylpyrrolidone)−Bromine Complex.

A poly(vinylpyrrolidone)−bromine complex (PVP−Br2) was easily prepared and used as a mild and convenient reagent for the selective bromination of alkenes and at the α-hydrogen of active carbonyl compounds.1204 Mokhtary et al. described the poly(vinylpyrrolidone)−bromine complex as an efficient reagent for the bromination of electron-rich aromatic compounds. The reaction proceeded smoothly with phenols and N,N-alkylated amines to afford the corresponding

Golding and Senear reported the use of phosphorus oxybromide as a reagent for the bromination of hydroxypyrimidines.1212 A number of new bromopyrimidines, with bromine in the 2-, 4-, and 6-positions, were reported. Direct fusion of the reactants led to the formation of 2,4,6tribromopyrimidine, 2-amino-4-bromopyrimidine, 2-amino6917


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and oxone in CH3CN/H2O (1:1) without employing a catalyst.1219 The reaction proceeded at ambient temperature in yields ranging from moderate to excellent without a catalyst. Vanadium(V) oxide catalyzes the in situ oxidation of NH4Br to provide the bromenium (Br+) ion.1220,1221 Choudhury et al. have shown a chemoselective monobromination of unsubstituted β-keto esters by using a combination of vanadium pentoxide, hydrogen peroxide, and ammonium bromide in a biphasic system, dichloromethane−water, at 0−5 °C. Cyclic βketo esters and 1,3-diketones can also be brominated selectively using the same protocol. They found that, for 1 equiv of the substrate, the use of 1.5 equiv of ammonium bromide, 0.5 equiv of vanadium pentoxide, and 19 equiv of hydrogen peroxide can provide the best result in a mixed medium of dichloromethane and water. Vanadium pentoxide helps in the formation of peroxo complexes, which oxidize the bromide ion to the bromonium ions and promote enol formation by chelating with the two carbonyl groups of the β-keto ester or 1,3-diketone (Scheme 430).1220

4,6-dibromopyrimidine, and 2-amino-4-bromo-6-methylpyrimidine in moderate yields, and 2-(p-nitrobenzenesulfonamido)-4bromo-6-methylpyrimidine was obtained in good yield when the reaction was carried out employing toluene as a diluent. 3.3.3. Triphasic System of Bu4N+HSO4−, NaBr, and NaOCl. Correia prepared the liquid triphasic system from Bu4N+HSO4−, NaBr, and aqueous NaOCl.1213 The third, interfacial layer was hydrophobic in character and consisted largely of Bu4N+Br3−. The system had brominating and oxidizing properties. The system could brominate a variety of compounds, such as cyclohexene, 1-octyne, 1-heptyne, phenylacetylene, deoxybenzoin, etc. Cyclohexene produces a mixture of trans-l,2-dibromocyclohexane and trans-l-bromo-2-chlorocyclohexane (Scheme 428). However, 1-alkynes react to produce 1-bromo-1-alkynes. Scheme 428

Scheme 430

3.3.4. Ammonium Bromide. Ammonium bromide can also be used as a brominating agent. Krishna Mohan et al. reported a method for the selective monobromination of anilines and anisoles using NH4Br as a bromine source and H2O2 as an oxidant (Scheme 429).1214 Efficient bromination of Scheme 429

In addition, α-monosubstituted β-keto esters, cyclic β-keto esters, and 1,3- diketones were also brominated selectively using the same protocol. α-Bromoalkanones were synthesized by reacting alkanones with ammonium bromide and ammonium persulfate in high yields using an aqueous grinding technique.1222 Another method for the selective α-monobromination of aralkyl, cyclic, and acyclic 1,3-diketones and β-keto esters and α,α-dibromination of 1,3-diketones and β-keto esters without a catalyst was reported by Macharla et al. using NH4Br and oxone.1223 The reaction proceeded at ambient temperature with a moderate to excellent yield. Bromination of unsymmetrical ketones took place at the less substituted α-position predominantly. Aromatization of tetralones was also carried out using this reagent system. 3.3.5. Iodine Monobromide. In 1938, Militzer reported that IBr is a mild brominating agent for substitution on the aromatic ring.1224 He showed that, in the preparation of 4bromo-1-naphthol and α-bromonaphthalene, iodine monobromide presented advantages over the regular bromination procedures. Phenol was brominated readily in a carbon tetrachloride solution to produce p-bromophenol in good yield. This reagent was also found to be quick and smooth in the bromination of α-naphthol to give good yields of 4-bromo1-naphthol (Scheme 431). Bennett and Sharpe repeated Militzer’s experiments with iodine monobromide with nitrobenzene as the solvent and phenol and salicylic acid as the substances to be brominated. They found that the organic products contained no more than

aromatic substrates with good yields and regioselectivity was observed with acetic acid as the solvent. The bromination is highly para-selective for aniline itself as well as for ortho- and meta-substituted anilines. Para-substituted anilines were brominated in the ortho position. The yields were generally good to excellent. They also described the high regioselectivity in the ring bromination of several methoxy derivatives of benzene and naphthalene. These systems yield selectively para-brominated aromatics unless the para position is substituted. They also extended this protocol for oxybromination of anilines and anisoles without a catalyst. Aromatic ethers were conveniently brominated with quaternary ammonium bromide and iodosylbenzene in glacial HOAc under mild conditions to give the corresponding monobromo aromatic ethers in nearly quantitative yields.1215 Tinidazole was synthesized from metronidazole by bromination with ammonium bromide in sulfuric acid, thioetherification with S-ethylisothiourea, and oxidation with hydrogen peroxide in a total yield of 42%.1216 The use of oxone as an oxidant in combination with NH4Br can be a good method for the generation of bromine in a reaction. This strategy was disclosed by Narender et al. for the selective monobromination of various activated aromatic compounds.1217 A similar strategy for the selective bromination of activated aromatic compounds using NH4Br as the bromine source and oxone as the oxidant in MeOH or an aqueous solution was reported by Kumar et al.1218 Macharla and coworkers used the combination of ammonium bromide and oxone for the synthesis of bromohydrins. Various olefins were regio- and stereoselectively hydroxybrominated using NH4Br

Scheme 431

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Scheme 432

different results with different catalysts. In the monobromination of aromatics, a milder catalyst, such as elemental iron, was used to keep chlorination and byproduct formation at a minimum. Bromine chloride also adds to the olefinic compounds to give the bromochlorinated product (Scheme 434).1236

a trace of iodine. At the end of the reaction between iodine bromide and phenol, a large quantity of iodine was precipitated.1225 In the study of steroid chemistry, the bromination of steroids was widely investigated using this reagent. IBr was found to be an effective reagent in the asymmetric monobromination of steroid aldehydes. Yanuka and co-workers reported that iodine bromide effected the monobromination cholanal, norcholanal, and 3α-acetoxynorcholanal in high yields (Scheme 432).1226 Adamantane when refluxed with IBr in CCl4 for 3 h produced 1-bromo- and 1,3-dibromoadamantanes in a 3:1 ratio with a combined yield of 99%.1227 Microwave irradiation accelerates the bromination of 1,4-quinones and coumarins with iodine monobromide in acetic acid as compared to the reactions run at room temperature.1228 Bromination took place selectively at the active quinonoid position in 1,4-quinones and at the α,β-double bond in coumarins. 3.3.6. Boron Tribromide. A method for the benzylic bromination of toluene derivatives was developed. Various substituted toluenes were brominated with boron tribromide as the bromine source in carbon tetrachloride at room temperature, affording their corresponding benzyl bromides in good yields (Scheme 433).1229

Scheme 434

Bromination of saccharin sodium salt with BrCl is a useful method for the production of N-bromosaccharin.1237 Unreactive alkenes, such as 1,2-di-, tri-, and tetrahaloethylenes or phenylethylenes, were halogenated using BrCl in the presence of tetrabutylammonium bromide as a phase transfer catalyst in an aqueous phase.1238 Nonn prepared 4-bromobiphenyl and 4,4′-dibromobiphenyl by the bromination of biphenyl with bromine chloride in good yield.1239 The reactions were carried out by adding BrCl at 5 °C to biphenyl in dichloromethane and stirring at room temperature. The addition reactions of bromine chloride with α,β-unsaturated methyl esters under ionic conditions were also studied. The reactions were carried out in CCl4 at 0 °C. BrCl addition gave mainly the 2-bromo-3chloro compounds.1240 3.3.8. Thionyl Bromide. Al-Mousawi et al. reported that SOBr2 reacts with aromatic ketones bearing α-protons or active methylene groups to produce either α-bromo ketones or α,αdibromo ketones in 60−80% yields. Thus, acetophenone was treated with SOBr2 in benzene to give 81% α,α-dibromoacetophenone (Scheme 435).1241

Scheme 433

A new bromination of methylarenes was developed by Shen et al. through boron tribromide under mild conditions, which is different from the traditional free radical processes.1230 The advantage of this method is the good yield and high selectivity. During the investigation of electron and steric effects, it was found that substrates with various substitutional groups could give the expected products in moderate to good yields. An electron-donating substitutuent was found to have a favorable effect on bromination, while an electron-withdrawing group decreased the yield. 3.3.7. Bromine Chloride. Bromine chloride is a good alternative to bromine. In 1958, Schulek and Burger reported bromine chloride exclusively as a brominating agent. They observed reactions with some aromatic compounds.1231 The same reagent has also been used for the determination of unsaturation in organic compounds.1232−1234 Boudakian carried out the vapor-phase bromination of pyridine with bromine chloride to give 2-bromopyridine (75%) as the major product.1235 In this process, 2-chloropyridine, 3-bromopyridine, and 2,6-dibromopyridine were also formed as side products. BrCl can brominate most aromatic compounds, such as benzene, phenols, anisole, toluene, cresols, salicylic acids, etc. Most of these reactions were carried out in chlorinated solvents such as methylene chloride at temperatures between 0 and 40 °C. The reaction of BrCl with aromatic compounds gave

Scheme 435

Al-Omran et al. treated anilides and p- and o-methoxyphenols with SOBr2, producing monobromo substitution products in quantitative yield. On the other hand, aromatic ethers reacted with SOBr2 only in the presence of AlCl3, yielding a mixture of ortho and para isomers in a 2:3 ratio. Thus, reaction of 4-MeOC 6H 4 OH with SOBr2 gave 91% 2-bromo-4methoxyphenol, whereas reaction of anisole with SOBr2 in the presence of AlCl 3 gave a mixture of o- and pbromoanisoles.1242 Saraf reported the reaction of thionyl bromide with benzoin to give α,α-dibromodeoxybenzoin in 66% yield (Scheme 436).1243 6919


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Scheme 436

The same group also investigated the action of SOBr2 on various alkanoic and alkenoic acids and benzoic acid. They found that alkanoic and chloroalkanoic acids, when reacted with thionyl bromide, produce the corresponding acid bromides in good yields (Scheme 439).1252

Benzaldehydes were treated with SOBr2 to yield benzylidene bromides. Thus, 4-isopropylbenzaldehyde and SOBr2 produced 1-(dibromomethyl)-4-isopropylbenzene (Scheme 437), while

Scheme 439

Scheme 437

3.3.9. Bromine Fluoride. Rozen and Brand used BrF as an efficient electrophilic brominating agent to brominate activated as well as deactivated aromatic rings.1253 This reagent was used without any catalyst. Bromine monofluoride was prepared by passing diluted fluorine (about 10% F2 in N2) through a cold (−75 °C) suspension of bromine in CFCl3. A solution of an activated aromatic substrate, such as toluene, anisole, etc., in a small amount of CHCl3 at −75 °C was added to a 5−10% excess of the BrF solution at −75 °C. Anisole was brominated quantitatively (in a para/ortho ratio of 4:1). Toluene was also monobrominated in >90% yield (para/ortho ratio of 1:1). With less activated aromatic rings, such as phenyl acetate or bromobenzene, quantitative para bromination was observed. In all these cases full conversion of the starting material was achieved in 5−15 min. Ethyl benzoate was converted into ethyl m-bromobenzoate in 95% yield. Sensitive groups such as aldehydes were not affected by the reagent, and benzaldehyde was transformed to m-bromobenzaldehyde in >90% yield. Even m-dinitrobenzene was brominated in 45 min without any catalyst, forming the expected 1,3-dinitro-5-bromobenzene in 93% yield (Scheme 440).

2- and 4-methylbenzaldehydes produced brominated benzylidene bromides. Benzenedicarboxaldehydes were converted to 1,4-bis(dibromomethyl)benzene, and 4-bromo-2-(dibromomethyl)-1-methoxybenzene was obtained from 2-methoxybenzaldehyde. However, 4-methoxybenzaldehyde and 3-hydroxy-4methoxybenzaldehyde produced 4-methoxybenzoic acid and 6bromo-3-hydroxy-4-methoxybenzaldehyde, respectively.1244 The same researcher reported that treatment of 2methoxybenzaldehyde with SOBr2 produced 4-bromo-2(dibromomethyl)-1-methoxybenzene, whereas, under the same reaction conditions, 4-methoxybenzaldehyde was converted to a mixture of 4-methoxybenzoic acid and 3-bromo-4methoxybenzoic acid.1245 He also reported that 4-halobenzenethiols and 4-methylbenzenethiol reacted with SOBr2 at room temperature to yield the respective disulfide. However, heating of PhSH with SOBr2 in benzene could yield diphenyl sulfide. Thus, 4-IC6H4SH was treated with SOBr2 at room temperature to give (4-IC6H4)2S2.1246 Heating a mixture of benzaldehyde or its 2- or 4-halo derivative with SOBr2 at 80−90 °C for 3 h gave the corresponding benzoyl bromides in 75−96% yield. A similar reaction of o-methylbenzaldehyde produced 1-(dibromomethyl)-2-methylbenzene, whereas cinnamaldehyde, ohydroxybenzaldehyde, and veratraldehyde gave the α-, 5-, and 6-bromo derivatives, respectively.1247 SOBr2 can also be used for the bromination of various phenolic substrates at 5 °C to produce the corresponding 4-Br-substituted phenols in 37− 40% yield.1248 However, the reaction requires the temperature to be raised in the case of para-substituted phenols for the synthesis 2-bromo derivatives. Moreover, the reaction could produce a 38% yield of the ortho-brominated product. Tropolone and phenol react with thionyl bromide, forming 3,7-dibromotropolone and 2,4-dibromophenol, respectively.1249 Treatment of pyrocatechol with SOBr 2 produces the corresponding 4,5-dibromo derivative, whereas hydroquinone reacts with SOBr2 to produce the 2,5-dibromo derivative.1250 Again, this reagent can be used for the bromination of unsaturated carboxylic acids. Saraf and co-workers synthesized dibromides of various unsaturated carboxylic acids such as maleic acid, fumaric acid, and cinnamic acid in quantitative yield (Scheme 438).1251

Scheme 440

Rozen and co-workers again carried out a detailed study about the utility of BrF for electrophilic bromination and dibromination of a broad spectrum of aromatic compounds (Scheme 441).1254,1255 The method was general, addition of Scheme 441

catalyst was not required, and it could offer excellent yields, short reaction times, and very mild conditions. When reacted with toluene at −75 °C, in ethanol, 2- and 4-bromotoluenes were formed in a 1:1 ratio. p-Xylene and anisole also gave mono- and dibrominated products, while, with compounds in which the ortho position was less accessible, e.g., tertbutylbenzene, phenyl acetate, and bromobenzene, only the pbromo derivatives were obtained in yields exceeding 90%. After a 5 min reaction at −40 °C, acetophenone was fully converted to 3-bromoacetophenone. The reaction was also found to

Scheme 438

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same reagent combination was found to be very effective in the bromination of a number of aromatic substances. They assumed that the positive halogen reagents were produced in situ for electrophilic bromination of the aromatic ring. They selected methanol as the solvent because of good solubility and suitable polarity.1265 They elaborated their studies to alkenes and alkynes also (Scheme 443).

proceed smoothly with aromatic compounds possessing both an electron-withdrawing and an electron-donating group. Methyl 4-methylbenzoate and 4-methylnitrobenzene reacted with a slight excess of BrF at −40 °C for about 1 h and were converted almost quantitatively to the corresponding 3-bromo derivatives. 3.3.10. Bromine Triflouride. In 1989, Lerman and Rozen established bromine triflouride as a brominating agent.1256,1257 They found that bromine trifluoride in a mixture with elemental bromine could be used as a bromination agent for deactivated aromatic compounds. The method comprised reacting an equimolar mixture of elemental bromine and bromine trifluoride with the aromatic compound, practically at room temperature. In all cases demonstrated, the reaction was instantaneous and no catalyst was required. In most cases, when an electron-withdrawing group was attached to the aromatic ring, the bromination took place at the expected meta position. The bromination method could be particularly applicable when extremely deactivated rings such as dinitrobenzenes and nitroacetophenones had to be brominated. Later, they extended the procedure to a variety of alkenes and α,β-unsaturated carbonyl compounds. These compounds were reacted with BrF3 to form vicinal bromo fluoro compounds. In most cases, the reactions followed a Markovnikov regioselectivity and antiaddition stereospecifity. They proceeded well even with deactivated olefins in 70% yield.1258 3.3.11. HBr. In 1942, Couper et al. studied the action of HBr in acetic acid on unsaturated 1,4-diketones. They found that HBr in acetic acid acted not only as a brominating agent but also as a reducing agent. Hydrogen bromide in acetic acid reacted with four 1,4-diaryl-2,3-dimethyl unsaturated 1,4diketones. In two cases the result was essentially reduction, and in the other two the result was both reduction and bromination in the para position of a phenyl group.1259 For example, for trans-1,2-dibenzoyldimethylethylene, the bromine entered the para position of one of the phenyl groups, and at the same time reduction occurred (Scheme 442).

Scheme 443

Espenson et al. tried methyltrioxorhenium (MTO) catalysis in the bromination of alkynes by the combination of H2O2 and HBr. Diphenylacetylene, methylphenylacetylene, and phenylacetylene were brominated by this method. The transdibromoalkene is favored in this case (Scheme 444).1266 Scheme 444

Again, various substituted toluenes were brominated at the benzyl position by an aqueous solution of hydrogen peroxide and hydrogen bromide illuminated by a 40 W incandescent light bulb.1267 Phenols were also brominated rapidly by H2O2, HBr, and MTO. These reactions exhibited a preference for bromination at the para position. Bromination did occur, however, when only the meta position was available. The selectivity in general follows the order para > ortho > meta.1Arylethanones and related compounds were brominated in dioxane with the H2O2−HBraq system by Terent’ev et al.1268 The two hydrogen atoms in the methyl group were replaced with bromine (Scheme 445). The reaction was also

Scheme 442

Scheme 445 On the other hand, when the cis-and trans-bis(p-bromophenyl) unsaturated diketones were treated with hydrogen bromide−acetic acid, the furan was produced in good yield. These results involved both reduction and dehydration. Davis et al. used HBr to prepare brominated pentaerythritols. They carried out the reaction at a temperature of about 100 °C by reacting pentaerythritol with HBr in acetic acid based on the pentaerythriol.1260 In the presence of a suitable oxidant, HBr can effectively brominate various organic frameworks.1261−1264 Barhate et al. studied a combination of aqueous tert-butyl hydroperoxide (TBHP) (70%) or hydrogen peroxide (34%) and a hydrobromic acid as an effective reagent for the bromination of aromatic compounds. They observed smooth bromination in boiling methanol without any catalyst for both of these oxidants. A number of different aromatic substrates were subjected to the bromination reaction to test the generality of this method. They found that efficient bromination of aromatic substrates took place with good yields and regioselectivity with TBHP and hydrobromic acids.1261The

accompanied by the bromination of the aromatic ring provided that the latter contains electron-donating substituents. The reaction proceeded rapidly (20 min) and resulted in complete conversion of ketones to give 2,2-dibromo-1-arylethanones in yields up to 86%. Podgoršek et al. reported the α-bromination of various 1,3diketones, β-keto esters, cyclic ketones, and aryl alkyl and dialkyl ketones effectively with an aqueous H2O2−HBr system “on water” at room temperature without the need for a catalyst or organic solvent (Scheme 446).1269 The resultant brominated ketones were isolated in yields of 69−97% with high selectivity for monobromination versus dibromination. Treatment of 1-arylbut-2-enes using a mixture of HBr and H2O2 leads to electrophilic addition of bromine or hypobromous acid at the side chain double bond (Scheme 6921


Chemical Reviews

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is more economic and easy to handle and offers sufficiently high regioselectivity (100%) for bromohydrin synthesis. Further activation of bromohydrin with a catalytic amount of HBr (50 mol %) and H2O2 in water affords α-bromo ketones in moderate to good yields in a single step.1272 3.3.12. Bromoiodinanes. Amey et al. first synthesized the stable crystalline bromoiodinanes and then used them as selective free radical brominating agents.1273 They prepared two bromoiodinanes by reacting the respective alcohols with bromine (Scheme 450).

Scheme 446

447). Under more severe conditions, the process is accompanied by the bromination of the aromatic ring.1270 Scheme 447

Scheme 450

Again, treatment of the 1-arylbut-2-enes with peroxy acids (RCOOH−H2O2) gives the corresponding epoxy derivatives, which react with HBr and oxygen-containing nucleophiles to produce α-bromo alcohols (Scheme 448).

Both bromoiodinanes gave highly selective allylic and benzylic free radical brominations. Irradiation in the presence of toluene or cyclohexene gives benzyl bromide (Scheme 451) or 3-cyclohexenyl bromide, respectively.

Scheme 448

Scheme 451

Braddock et al. prepared bromoiodinanes conveniently and directly from iodobenzenecarbinols and N-bromosuccinimide.1274 They characterized these bromoiodinanes crystallographically for the first time. They also found that these compounds acted as electrophilic bromine donors. 3.3.13. Alkyl Hypobromites. Heasley reported the bromination of nitroalkanes with alkyl hypobromites in the presence of an alkene (Scheme 452). When they added tertbutyl hypobromite to 1-hexene in nitromethane, three products were formed, namely, bromonitromethane, dibromonitromethane, and tribromonitromethane. Here the olefin played the catalytic role.1275 Again, Ody et al. studied the liquid-phase bromination of 1bromo- and 1-chlorobutane using tert-butyl hypobromite as the brominating agent.1276 This reagent produced a mixture of 1,2and 1,3-dibromobutanes. 3.3.14. Natural Sources. 3.3.14.1. Seaweed. Wever et al. reported some seaweeds which contain bromoperoxidases. These are the brown seaweeds Laminaria saccharina, Laminaria digitata, Fucus uesiculosis, Pelvetia canaliculata, and Ascophyllum nodosum and the red seaweeds Chondrus crispus and Plocamium hamatum. The intact plants are able to brominate organic compounds when H2O2 and Br− are added to seawater. The brown macroalga A. nodosum shows brominating activity when the plant is exposed to light and not in the dark.1277 3.3.14.2. Enzymes. Myeloperoxidase and eosinophil peroxidase were able to brominate deoxycytidine, a nucleoside, and uracil, a nucleobase, at plasma concentrations of Br− (100 μM). The two enzymes used different reaction pathways.1278 For example, the myeloperoxidase system of human neutrophils generates brominating oxidants that convert uracil into 5bromouracil and transform deoxycytidine into 5-bromodeoxyuridine (Scheme 453).

A method of bromination was reported by Gavara et al. using the isoamyl nitrite/HBr system.1271 The reaction succeeded with slightly activated arenes and heterocyclic compounds. The isoamyl nitrite/HBr mixture was also utilized for bromination in the α-position of electron-withdrawing groups (Scheme 449). They carried out the bromination reaction with different Scheme 449

activated and inactivated aromatics, as well as compounds of moderate activity. All reactions were realized at room temperature by using 2 equiv of isoamyl nitrite and 1.5 equiv of 48% HBr. Under these conditions, no regioselectivity was observed for electron-rich N,N-dimethylaniline or phenols, which led to a mixture of mono- and polybrominated products. 1,2-(Methylenedioxy)benzene gave a quantitative amount of 4bromobenzodioxole, and reaction of less activated naphthalene yielded 85% 1-bromonaphthalene in 8 h. The reaction with toluene led to an 84% yield of an 80:20 mixture of pbromotoluene/o-bromotoluene. Less reactive arenes such as chlorobenzene or 4-methoxyacetanilide did not react in these conditions. Patil et al. used the HBr−H2O2 system for the regioselective synthesis of bromohydrins and α-bromo ketones under mild aqueous conditions. HBr−H2O2 is efficiently activated in water under mild conditions. Therefore, they carried out the bromohydroxylation reactions of various styrenes. HBr−H2O2 6922


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Scheme 452

developed a procedure for the synthesis of vicinal bromo azides from alkene by the addition of bromine azide generated from bromine and sodium azide.1283−1285 The reaction was carried out by adding bromine to an ice-cooled and stirred mixture of sodium azide, 100 mL of either methylene chloride or pentane, and 25 mL of 30% HCI. The solution of bromine azide thus produced was separated and directly used for further reaction with olefin for bromo azide synthesis. This procedure requires the use of excess hydrazoic acid to suppress the formation of dibromo compounds. Hall and Jones developed a process for the addition of BrF to alkenes by using a combination of bromine and silver monofluoride.1286 The reaction was effected by in situ generated BrF in benzene at room temperature. Brand and Rozen found that the direct action of fluorine on bromine at −78 °C produces BrF, which adds readily across various double bonds provided there is some hydrogen donor in the reaction mixture.1287,1288 In general, this reaction works well in chloroform in the presence of a trace amount of alcohol, and only trans bromofluorination was observed. They also found that, when the reaction was applied to enonsan, easy elimination of HF took place, thus producing α-bromo enones.

Scheme 453

4. COHALOGENATION REACTIONS 4.1. Cohalogenation Reactions Using Molecular Bromine

Bromohydroxylation of 1,2-allenyl sulfides or selenides with bromine and water was carried out, and good regioselectivity was observed. This led to the synthesis of synthetically important 3-organosulfur or seleno-2-bromoallylic alcohols.1279 Bromohydroxylation of allenyl sulfides was carried out with bromine in aqueous acetonitrile in the presence of Na2CO3 (Scheme 454).

4.2. Cohalogenation Reaction with NBS

Guss et al.1289 carried out a reaction of olefins with NBS in water to form bromohydrins. The olefin and NBS in water were stirred vigorously, and after a short time period, the bromohydrin was formed. In all reactions, the disappearance of the NBS was a good sign of the progress of the reaction. Olefins such as styrenes, cyclohexene, trimethylethylene, 1,4dihydronaphthalene, indene, and cinnamic acid also gave the bromohydrin product. Tetrachloroethylene, crotonaldehyde, cinnamaldehyde, and benzalacetophenone were also used in this reaction, but it was not successful. Later, Dalton and coworkers improved the method of bromohydrin synthesis using NBS and moist DMSO.1290,1291 A number of olefins could be converted to the corresponding bromohydrins using this procedure in moderate to high yield. Yadav and co-workers further improved this procedure for NBS-assisted bromohydrin synthesis using the ionic liquid [bmim]BF4 as a recyclable reaction medium.1292 They carried out the reaction by treating NBS with olefin in a mixture of [bmim]BF4 and water at room temperature to obtain bromohydrins in excellent yield (Scheme 456).

Scheme 454

Heasley et al. studied the bromination of olefins with bromine in dimethyl sulfoxide and methanol in several proportions.1280 It was found that solvent incorporation produced an intermediate sulfonium ion. Bromination in DMSO− methanol gave methoxy bromide. The bromohydrin was formed by the addition of the bromination product to water. In a new synthetic route to β-carbolines, described by Love, in an intermediate step, molecular bromine was used for bromination.1281 Here, alkenesulfonamides were converted to the corresponding alkoxy bromide compound using bromine and methanol in dichloromethane as the reaction medium (Scheme 455). Scheme 455

Scheme 456

The products of bromine addition in acetic acid have been investigated for a series of ring- and side-chain-substituted styrenes and for cis- and trans-2-butenes.1282 It was found that the styrenes produced substantial amounts of 1-acetoxy-2bromo derivatives as well as the expected 1,2-dibromides, but the butenes give almost exclusively dibromide under the same conditions. The additions to the styrenes are nonstereospecific. In most cases, trans addition is favored and additions to cis- and trans-2-butenes are found to be completely stereospecific. Acetoxy bromide formation was found to be more stereoselective than dibromide formation. Hassner and Boerwinkle

We have used iodine as an efficient catalyst along with NBS for the synthesis of anti-bromohydrins at low temperature. The method is high yielding, and cinnamic esters were found to be suitable substrates under the reaction conditions.1293 Hydroxybromination of methyl oleate, oleic acid, and sunflower oil was studied by Eren and Küsefoğlu in an acetone/water mixture using NBS (Scheme 457). The yield of bromohydrin products from oleic acid, methyl oleate, and sunflower oil were 90%, 78%, and 40%, respectively.1294 6923


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and water in THF at 20 °C (Scheme 461).1299 This resulted in the selective formation of the corresponding bromohydrins.

Scheme 457

Scheme 461

A mixture of DMSO and water is also a useful solvent system for bromohydrin formation in the presence of NBS. For example, 1-phenylcyclohexene could be transformed into the corresponding bromohydrins at room temperature using NBS in a mixture of DMSO and water1295 (Scheme 458).

In the synthesis of 2-aminothiazole-5-carboxylates, the reaction of ethyl β-ethoxyacrylate with NBS produced an intermediate, α-bromo-α-formylacetate hemiacetal.1300 Cyclization of the in situ formed hemiacetal with thioureas afforded 2aminothiazole-5-carboxylates in 60−98% yields (Scheme 462)

Scheme 458

Scheme 462

Yang et al. prepared a variety of (bromocyclopropyl) methanol and 3-bromobut-3-en-1-ol derivatives via the simple bromohydroxylation reaction of alkylidenecyclopropanes using NBS as the bromine source.1301 The reaction was carried out with 2 equiv of NBS in aqueous acetone at room temperature. Langman and Dalton synthesized erythro-2-bromo-1,2-diphenylethanol from (E)-stilbene in a mixture of water and dimethyl sulfoxide using NBS at room temperature.1302In the stereoselective synthesis of chiral tertiary alcohol building blocks, Raghavan utilized NBS as the brominating agent.1303 For this, the olefinic substrates were prepared as an equimolar mixture of epimers by condensing the lithium anion of methyl p-tolyl sulfoxide and unsaturated aldehydes. The anti and syn isomers were separated, and reactions were carried out with 1.2 equiv of NBS and 1.5 equiv of water in toluene as the solvent (0.2 M) (Scheme 463).

However, under the same reaction conditions, 1-phenylcyclooctene and 1-phenylcycloheptene with NBS in aqueous DMSO give the corresponding 3-bromo-2-phenylcycloalkenes and 2-phenylcycloalk-2-enols in a ratio of 3:1. The reaction of 1-phenylcyclooctene proceeds via the formation of bromohydrin. Kalmefound that the treatment of 3,4-dihydropyridin2(1H)-ones with NBS in ethanol in the presence of benzoyl peroxide led to the formation of the corresponding bromohydrins.1296 Hanzlik used NBS for the synthesis of bromohydrin in the presence of water, where he could differentiate one of the three olefinic bonds of 3,7,11trimethyldodeca-2,6,10-trienyl acetate. He found that the action of NBS on the substrate in a mixture of tert-butanyl alcohol and water produced the corresponding 10-bromo-11-hydroxy3,7,11-trimethyldodeca-2,6-dienyl acetate as the exclusive product (Scheme 459).1297

Scheme 463

Scheme 459

Tello-Aburto reinvestigated the bromohydrin reaction in Grieco’s bicyclic lactone.1304 Two regioisomeric bromohydrins were obtained, and their configurations were unambiguously determined by X-ray diffraction analyses. The reaction of NBS and acetic acid with olefins such as 1-octene, 2-octene, 1decene, 1-dodecene, 1-hexadecene, styrene, cyclohexene, and indene was investigated by Iovchev.1305 It was found that the corresponding bromoacetoxylated derivatives were formed during the reaction. He also carried out the addition of NBS and methanol to 1-octene, 2-octene, 1-decene, 1-undecene, 1dodecene, 1-tetradecene, 1-hexadecene, cyclohexene, and indene. This time he found the formation of a mixture of bromomethoxylated derivatives.1306 Chen et al. developed a procedure for the bromolactonization of γ,δ-unsaturated acids and bromoacetoxylation of olefins using molecular sieves as the catalyst and NBS as the bromine source (Scheme 464).1307 The bromolactonization was carried out by adding NBS to a mixture of γ,δ-unsaturated acids and molecular sieves (20 wt %) in dichloromethane at room temperature. Lactones were formed

In the stereoselective synthesis of (2R,3R)- and (2R,3S)-3hydroxyleucine, the key step of the reaction sequence involves stereo- and regioselective bromohydration of a compound.1298 This was achieved by using a brominating agent derived in situ from NBS and 2,6-lutidine, via intramolecular sulfinyl group participation (Scheme 460). The key steps associated with the generation of the epoxyquinol synthons from the cis-1,2-dihydrocatechol starting materials involved the treatment of each halodiene with NBS Scheme 460

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preparation of bromoalkoxylated methacrylates has also been reported by Fort and Gottardidubosclard.1316In a study of the bromination of cinnamic acid in aqueous methanol with NBS, it was found to form 2-bromo-3-methoxy-3-phenylpropionic acid.1317 The reaction was inhibited by succinimide. The reaction rate decreases with an increase in the methanol content of the medium. An efficient one-pot procedure was described by Lichtenthaler et al.1318 for the conversion of a variety of hydroxyglycal esters to their 2-oxoglycosyl bromides, which simply comprises brief treatment with NBS/methanol at ambient temperature. The synthesis of surfactants from 1olefins via bromoalkoxylation reaction in the presence of NBS was described by Okahara.1319 α,β-Unsaturated ketones were brominated by Heasley and co-workers using NBS.1320 They found that the bromination α,β-unsaturated ketones such as methyl vinyl ketone, phenyl vinyl ketone, (E)-3-penten-2-one, methyl isopropenyl ketone, 2-cyclohexen-1-one, 1,4-benzoquinone, etc. react with NBS in methanol to produce a mixture of methoxy bromides and α,β-dibromo ketones (Scheme 467).

Scheme 464

as the exclusive product from the reaction. Similarly, bromoacetoxy products were made by reacting molar equivalents of NBS and acetic acid in DCM at room temperature. The efficacy of NBS toward the asymmetric intermolecular bromoesterification of unfunctionalized olefins with carboxylic acids has also been examined.1308 Dimethylformamide (DMF) is shown to react in a stereospecific and regioselective fashion with bromonium ions, generated from a variety of olefins and NBS in the presence of water.1309 The reaction generated the corresponding bromoformates, which on hydrolysis produced bromohydrins as the final product. Yeung et al. developed a multicomponent aminoalkoxylation and alkoxyetherification process via a cyclic ether ring-opening cascade.1310−1312 They described the use of olefin, cyclic ether, amine, and Nbromosuccinimide for the aminoalkoxylation process (Scheme 465).1310 It is a one-pot reaction where the olefins and the cyclic ether were flexibly varied to produce a range of amino ether derivatives.

Scheme 467

They carried out the experiments with liquid bromine also and found that the ratios of Markovnikov to anti-Markovnikov regioisomers were increased when the brominations were conducted in the presence of NBS. Younes et al. reported that alkenes react in diethyl ether with NBS and dimercaptoethane to afford the corresponding β,β′dibromo dithioethers (Scheme 468).1321 This resulted from

Scheme 465

Scheme 468

Kim and Cha adopted an intramolecular bromoamidation strategy for the total synthesis of (−)-8,8a-di-epi-swainsonine.1313 In an intermediate step, they treated a 1-(tosylamino)4-hexene derivative with NBS to afford a 2-(1-bromoethyl)-1tosylpyrrolidine skeleton which was subjected to further synthetic manipulations to achieve the total synthesis. A method for the synthesis of 1,2,4-trisubstituted or 1,2,3,4tetrasubstituted 1,2,5,6-tetrahydropyridine was presented by Chang et al. The process was carried out by the bromomethoxylation of 4-substituted 1,2,5,6-tetrahydropyridines with NBS in methanol (Scheme 466).1314 This was

electrophilic bromination by NBS followed by dimercaptoethane addition to 2 mol equiv of olefins. In a similar way, Singh and Singh found that gemini surfactants (β,β′-dibromo dithioethers) can be produced by reacting olefinic fatty methyl esters with NBS and dimercaptoethane in diethyl ether.1322 The reaction of olefinic esters such as undec-10-enoate, octadec9(Z)-enoate, and methyl 12-hydroxyoctadec-9(Z)-enoate was carried out by adding dimercaptoethane to a mixture of the unsaturated ester and NBS in diethyl ether at 0 °C. The reaction was further continued at room temperature for 1 h, resulting in the β,β′-dibromo dithioethers in high yield. Baklouti later made a slight modification of this procedure for the one-pot conversion of olefins into the corresponding enol thioethers.1323 The products were obtained via the NBS cobromination reaction of olefins with thiols in a basic medium (Scheme 469). Olah and co-workers found that the use of hydrogen fluoride−pyridine in conjunction with NBS leads to the

Scheme 466

followed by dehydrobromination with 1,8-diazabicyclo[5.4.0] undec-7-ene (DBU), and boron trifluoride etherate (BF3− OEt2)-catalyzed cross coupling of the corresponding enamine with trimethylsilyl-based nucleophiles. Heasley et al.1315 carried out the reaction of but-3-en-2-one, 1-phenylprop-2-en-1-one, (E)-pent-3-en-2-one, acrolein, and methyl acrylate with NBS. The bromination reaction provides only α-bromo-β-methoxy adducts. In the absence of acid catalysis, only mesityl oxide reacts with NBS in MeOH to give the bromo methoxy adduct. A similar method for the

Scheme 469

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fluorination of aliphatic olefins with typical Markovnikov-type regioselectivity.1324 Similar regioselectivity was observed by Zupan in the case of the bromofluorination of 1-phenylcyclohexene with the same reagent combination.1325 The reaction is stereospecific and anti-selective. For example, bromofluorination of 2-phenyl-3-bromocyclohexene results in the formation of 1-bromo-2-fluoro-2-phenyl-3-bromocyclohexane with exclusive formation of the anti product. This procedure from bromofluorination using HF−pyridine or HF−THF was further extended by Hamman and Beguin for cinnamic esters.1326 Although the observed regioselectivity was Markovnikov-type, the stereoselectivity was found to be dependent on the type of substrate, solvent, and concentration of HF. However, the bromofluorination of allyl benzene under the same conditions resulted in the formation of both Markovnikov and anti-Markovnikov products in a 7:1 ratio.1327 The bromofluorination reaction was further developed by Chehidi et al. using NBS and triethylamine tris(hydrofluoride).1328 They found that the treatment of allylic alcohols using a combination of NBS and Et3N·3HF produces vicinal fluorobromohydrins in high yield. Mekini et al. extended this procedure for the bromofluorination of bis(allyl)poly(oxyethylene) glycol ethers.1329 Haufe et al. made an improvement of this procedure for the vicinal bromofluorination of alkenes using NBS and Et3N·3HF.1330−1332 The reaction was carried out by taking an olefin such as α-methylstyrene and triethylamine trihydrofluoride in dichloromethane at 0 °C using NBS as the bromine source (Scheme 470).

when used along with NBS. 4-tert-Butyl-1-methylcyclohexene using a combination of NBS and TBAF provided vicinal bromo fluorides. Similar treatment of methyl 3α,7α-diacetoxy-5β-chol11-ene-24-carboxylate afforded the 12α-bromo-11β-fluoro steroid in good yield. Yoshino et al.1337 have shown the use of an ionic liquid, namely, 1-ethyl-3-methylimidazolium oligo(hydrogen fluoride) (EMIMF(HF)2.3) along with NBS for the bromofluoroination process. They carried out the reaction in CH2Cl2 at room temperature using 2 equiv of NBS. The products were isolated with a very good yield. The method was reported for the bromoazidation of alkenes using bromine azide, which was generated in situ from NBS and NaN3.1338,1339 Olah employed NBS and trimethylsilyl azide ((TMS)N3) for the bromoazidation of alkenes in the presence of Nafion-H in DME/H2O.1340 Metal triflates were also used as catalysts for the 1,2-bromoazidation of alkenes using NBS and (TMS)N3 as the bromine and azide sources, respectively. This catalytic process represents a highly regioselective and stereoselective and high-yielding method for the synthesis of anti-1,2-bromo azides from a variety of alkenes, including α,β-unsaturated carbonyl compounds (Scheme 472).1341 Scheme 472

Scheme 470

The same group again carried out Lewis acid-catalyzed asymmetric bromoazidation of chiral α,β-unsaturated carboxylic acid derivatives using NBS and trimethylsilyl azide ((TMS)N3) as the bromine and azide sources (Scheme 473).1342 They reported Yb(OTf)3 as the best catalyst for this particular reaction.

Ernet and Haufe described the synthesis of 2-fluoroalk-1-en3-ols by the bromofluorination of terminal olefins,1333 subsequent dehydrobromination of the thus-formed bromo fluorides, and allylic hydroxylation of vinyl fluorides by SeO2 oxidation. (ω-1)-Fluoroalkan-ω-olides of medium to large ring size can easily be synthesized in a facile two-step procedure by the bromofluorination of terminally unsaturated fatty1334 acids with NBS/Et3N·3HF and subsequent cyclization with K2CO3 in dimethyl sulfoxide (Scheme 471).

Scheme 473

Our group has also developed a rapid and efficient method for the synthesis of vicinal bromo azide directly from an olefin using NBS and trimethylsilyl azide ((TMS)N3) as the bromine and azide sources, respectively, without any catalyst in acetonitrile as the solvent. The rate of reaction is remarkably fast in acetonitrile without a catalyst to produce bromo azides in high yield.1343 Actually, we intended to study the catalytic effect of iodine on the bromoazidation reaction using NBS as a bromine source. The initial reaction in DCM was promising. The reaction was found to be extremely fast in acetonitrile, producing the corresponding bromo azide in high yield (Scheme 474).

Scheme 471

Lubke and Haufe found that the regiochemistry of the bromofluorination of 1-alkenes with this reagent combination mainly depends on the character of the functional groups in the neighborhood of the double bond and only weakly on the fluorinating agent.1335 While monosubstituted terminal alkenes mainly yield Markovnikov-oriented products, electron-withdrawing groups in the allylic or homoallylic position to the double bond favor the anti-Markovnikov-oriented bromo fluorides. Moreover, with decreasing reactivity of alkenes, the formation of dibromides becomes a competitive side reaction of bromofluorination. Kojima1336found tetra-n-butylammonium fluoride (TBAF) to be an effective source for the fluoride ion

Scheme 474

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However, later we found that the reaction works very well without any catalyst in acetonitrile. When acetonitrile was used as the solvent, the reaction was complete instantaneously to produce the corresponding bromo azide in high yield. Various kinds of substrates such as styrenes, cyclohexene, and cinnamates could be converted to the corresponding bromo azides using this procedure. We found that the reaction is regioselective; however, moderate steroselectivity was obtained for most of the cases (Scheme 475).

nitroalkyl)carbamates in high yield under this reaction condition. Masson reported a highly enantio- and diastereoselective electrophilic α-bromination of enylcarbamates through a domino bromination/nucleophilic addition using NBS in the presence of chiral phosphoric acids or chiral calcium phosphates as catalysts.1347 The reaction proceeds under mild condition in the presence of a 1 mol % concentration of catalyst to provide enantioenriched vicinal haloamines (Scheme 479).

Scheme 475

Scheme 479

Zalkow carried out the bromination of bicyclo[2.2.1]-5heptene-endo-cis-2,3-dicarboxylic anhydride with NBS in the presence of benzoyl peroxide to yield the cis adduct, exo-5bromo-exo-6-succinimidobicyclo[2.2.1]heptanes, and endo-cis2,3-dicarboxylic anhydride (Scheme 476).1344 NBS rearranged

An interesting feature of this process is that the reversal of enantioselectivity for the catalytic bromination could be achieved simply by switching the catalyst from phosphoric acid to its calcium salt. Sudalai et al. developed an efficient method for the vicinal aminohalogenation of olefins using NBS as the bromine source using Cu, Mn, or V catalysts with p-toluenesulfonamide as the nitrogen source.1348 Excellent regio- and stereoselectivity is shown for different olefinic substrates as well as transition-metal catalysts. An interesting feature of this method is that the regioselectivity could be controlled by choosing the catalyst system. They found that the use of a Mn−salen complex produces the aminobromine with regioselectivity opposite that produced by using a mixture of CuI and MnSO4 as the catalyst (Scheme 480).

Scheme 476

under the reaction conditions to give β-bromopropionyl isocyanate, but isolation of a diacid from the original reaction mixture was found easier than isolation of the anhydride. Landesberg et al. synthesized trans-3-bromo-4-succinimidotetrahydrothiophene 1,1-dioxide from the 3-sulfolene.1345 The reactions were carried out using NBS in the presence of benzoyl peroxide in a carbon tetrachloride solution under refluxing conditions (Scheme 477).

Scheme 480

Scheme 477

Pan et al.1346 reported a method for the aminobromination of α,β-unsaturated nitro compounds with benzyl carbamate/ NBS as a new nitrogen/bromine source (Scheme 478). The

A convenient and efficient method for the aminobromination of alkylidenecyclopropanes was reported by Huang et al.1349 They achieved the stereoselective preparation of N-[(Z)-3bromobut-3-en-1-yl]-p-toluenesulfonamides by using p-toluenesulfonamide and NBS as the nitrogen and bromine sources, respectively (Scheme 481).

Scheme 478

Scheme 481

reaction was carried out by treating the substrate with NBS and CbzNH2 in the presence of K3PO4 (5 mol %) as the catalyst in acetonitrile at room temperature. A broad range of substrates, including aromatic and aliphatic compounds and heterocycles, were converted to the corresponding benzyl (2,2-dibromo-2-

Zhanguo developed a procedure for the aminobromination of β,β-dicyanostyrene derivatives with NBS as the aminobrominating reagent.1350 The process was carried out in the presence of NaOAc (10 mol %) as the catalyst in acetonitrile in an ice−water bath to convert β,β-dicyanostyrene derivatives into the vicinal haloamines with full regiospecificity and high stereoselectivity (Scheme 482). The aminobrominated prod6927


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ucts were obtained in excellent yields (up to 95%) under these conditions.

Raghavan et al. disclosed a method for the bromosulfonamidation of olefins using a combination of (S,S)-dimethyl-N(p-tolylsulfonyl)sulfilimine and N-bromosuccinimide as the bromide source.1362 They studied the synthesis of 3,4unsaturated disubstituted (E)- and (Z)-2-hydroxysulfilimines and their haloamidation reaction.1363 Here they used NBS for the regio- and stereoselective preparation of bromocarbamates. All reactions were performed using 0.5 mmol of the sulfilimine in the presence of 1.2 equiv of NBS and 1.5 equiv of water in toluene (0.2 M) at room temperature (Scheme 486).

Scheme 482

Wu et al. proposed a reaction with a series of olefins, including α,β-unsaturated ketones, cinnamates, cinnamides, and styrenes, for aminobromination with good yields and excellent diastereoselectivities under mechanical milling conditions, using TsNH2 and NBS as the nitrogen and bromine sources, promoted by (diacetoxyiodo)benzene (Scheme 483).1351

Scheme 486

Scheme 483

Aminohalogenation reaction of β-nitrostyrenes with Nbromosuccinimides was conducted by using nickel acetate as a catalyst in the presence of potassium carbonate and succinimide as coadditives (Scheme 487). The reaction was easily performed at room temperature under nitrogen gas protection to give the products in good to excellent yields (60%−98%).1364

They also achieved the same reaction using hypervalent iodine compounds as the promoter.1352 Later they also achieved aminobromination in water.1353 Wang et al. developed FeCl2-catalyzed aminobromination of alkenes using amides or sulfonamides and NBS as the nitrogen and bromine sources.1354 A similar aminobromination method has also been reported by Wei et al. using different catalysts such as silicon powder, KI, aluminum powder, and copper powder.1355−1358 Cai et al. developed the first catalytic regio- and enantioselective bromoamination of chalcones by chiral N,Ndioxide/scandium(III) complexes to afford α-bromo-β-amino ketone derivatives with excellent outcomes under mild reaction conditions. Here NBS was used as the brominating agent (Scheme 484).1359 The reaction proceeds via an unusual bromonium-based mechanism. The results were excellent with nearly quantitative yields, and up to 99% ee was obtained.

Scheme 487

Shaikh et al. proposed a procedure for the aminobromination of olefins using p-toluenesulfonamide and NBS as the nitrogen and bromine sources, respectively, and titanium superoxide as a truly heterogeneous catalyst. An anti-Markovnikov product was formed exclusively in all the cases.1365 A regio- and stereoselective cohalogenation process has also been achieved with alkynes.1366,1367 Chen et al. reported a silver-catalyzed bromoacetoxylation reaction of simple terminal alkynes (Scheme 488).1366 They synthesized β-bromo enol acetates

Scheme 484

Scheme 488

Under catalyst-free conditions, NBS can be suitably utilized with N-methyl-p-toluenesulfonamide and 4-(trifluoromethyl) benzenesulfonamide to achieve aminobromination.1360,1361 Zhang and co-workers developed a catalyst-free electrophilic aminobromination system with N-methyl-p-toluenesulfonamide (p-TsNHCH3) and NBS as the nitrogen and bromine resources, respectively (Scheme 485). The reaction can give vicinal haloamines in good yields and excellent regioselectivities and stereoselectivities under convenient and mild conditions.1360

using acetic anhydride and NBS in the presence of silver tetrafluoroborate as the catalyst. In most cases, the (Z)-βbromo enol acetates were obtained regio- and stereospecifically in moderate to excellent yields. In the presence of DBU, NBS can be used as a bromoaminating reagent with alkynes to achieve enamines.1367 Enamines can also be synthesized from electron-deficient olefins and β,β-dicyanostyrene derivatives in the presence of NBS.1368,1369 A regioselective bromohydroxylation reaction of simple allenes was studied by Kong et al.1370 The reaction was carried out by using NBS as the electrophilic reagent in a mixture of 1,4-dioxane/H2O (1:1) at room temperature (Scheme 489). Ma et al. synthesized chiral bromohydrins via asymmetric bromohydroxylation of 2-aryl-2-propen-1-ols in the presence of

Scheme 485

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et al. reported that α-bromo amides were obtained with NBS in the presence of 10 mol % InBr3.1376 The reaction was carried out with NBS and acetonitrile in the presence of 10 mol % InBr3. The reaction was completed in 10 min at room temperature (Scheme 493). The use of Lewis acid in bromoamidation significantly improved the yields and reaction rates.

Scheme 489

a quinine-derived bifunctional catalyst. The regioselectivity of the process was controlled by employing boronate ester as a tether that formed in situ.1371 The total synthesis of roquefortine C was achieved by Shangguan et al. by implementation of an elimination strategy to construct the thermodynamically unstable (E)-dehydrohistidine moiety.1372 To make the thermodynamically unstable E-isomer, one needed the threo isomer. To this end, the protected ester was treated with NBS in an acetonitrile/water mixture to afford the anti-β-hydroxy-α-bromo derivative (Scheme 490).

Scheme 493

A combination of mandelic acid and NBS efficiently converts prochiral alkenes into a readily separable 1:1 mixture of the bromomandelates (Scheme 494).1377 The reaction is carried Scheme 494

Scheme 490

out by adding the alkene to a mixture of (S)-mandelic acid and 2,6-lutidine in dry dichloromethane in the presence of NBS. The diastereomerically pure bromomandelates are then converted into a variety of enantiomerically pure products. In the diastereoselective synthesis of 3,4-dimethoxy-7morphinanone, Yamada treated 2-(2,3-dimethoxyphenyl)cyclohexen-1-ol with ethyl vinyl ether in the presence of NBS to give the bromo acetal as a mixture of two epimers (Scheme 495).1378 The reaction proceeds via the formation of a bromonium intermediate from ethyl vinyl ether and NBS, which transforms into the product due to the attack by the alcohol.

A halogen-promoted highly regio- and stereoselective Friedel−Crafts alkylation with alkenes was developed by Hajra et al. with the use of NBS as the halogen source.1373 Lewis acids, in particular metal triflates, were the catalysts for this reaction. Among these, Sm(OTf)3 was the best catalyst. They selected acetonitrile as the best solvent. One interesting feature of this reaction is that, in the absence of metal triflates, the reaction did not produce any Friedel−Crafts alkylated product (Scheme 491). Scheme 491

Scheme 495

The stereoselective synthesis of β-branched α-bromo carboxylic acids containing two newly formed chiral centers was accomplished by the 1,4-addition of dialkylaluminum chlorides to α,β-unsaturated N-acyloxazolidinones and subsequent reaction of the intermediate aluminum enolates with NBS (Scheme 492).1374 Butterick et al. carried out the reaction of NBS with 1-(η5C5H5)-2-Ph-closo-1,2,3,4-FeC3B7H9, resultin in selective bromination at the B-6 boron of the tricarbadecaboranyl ligand to form 1-(η5-C5H5)-2-Ph-6-Br-closo-1,2,3,4-FeC3B7H8.1375Yadav

Treatment of trans-cinnamyl alcohol with NBS in CH2Cl2 afforded the bromohydrin in 80% yield.1379 Radical cyclization of this bromohydrin with n-Bu3SnH and AIBN in refluxing benzene furnished the 5-exo-trig cyclized product (Scheme 496).

Scheme 492

Brabandt et al. used NBS for the ring expansion reaction.1380 4-Isopropenylazetidin-2-ones were added to a mixture of 1.3 equiv of NBS, 1.3 equiv of azidotrimethylsilane ((TMS)N3), and dichloromethane and nitromethane in a ratio of 3:1 by volume at room temperature (Scheme 497). Azidobromination of the starting compounds produced 5-azidopyrrolidin-2-ones in moderate to high yields.

Scheme 496

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Scheme 497

Scheme 500

phenyl-2-(p-toluenesulfonamido)-1-bromoethane. 1387They synthesized the corresponding amino bromine by treating TsNBr2 with an excess amount of styrene (Scheme 501).

The synthesis of vicinal bromohydrins from olefins was achieved by Rao et al. in the aqueous phase in the presence of β-cyclodextrin (Scheme 498).1381 The reaction was carried out

Scheme 501 Scheme 498

Treatment of the resulting 2-bromo-1-sulfonamid with a base led to the formation of aziridine. The same strategy was applied by Hegedus for the synthesis of some nitrogen heterocycles.1388 Terauchi and co-workers carried out reaction of TsNBr2 with 2methyl-3,4-dihydronaphthalene in a solution of dichloromethane at 0 °C to produce the amino bromine; however, the reaction yield was not very good (Scheme 502).1389

by adding NBS to a solution of the alkene and β-cyclodextrin (1 equiv) in a mixture of acetone and water at room temperature. Bromohydrins are formed in high regioselectivity and yield within a short time. A similar method of bromohydrin synthesis using NBS was reported by Das et al.1382 The reaction was carried out using ammonium acetate (NH4OAc) as the catalyst in a mixture of acetone and water as the reaction medium at room temperature. They also synthesized halo ethers using an alcohol as the solvent.

Scheme 502

However, the formation of the amino bromine was found to be more efficient if the reaction was carried out in the presence of Mn(OAc)2 with extra addition of p-toluenesulfonamide (Scheme 503).1390 The combination of TsNBr2 and TsNH2

4.3. Cohalogenation Reaction with Other Bromo-Organic Compounds

NBSac reacted with electron-deficient alkenes such as unsaturated ketones, acids, esters, and nitriles in aqueous organic solvents, yielding the corresponding bromohydrins in good yields. Alkenes in the presence of NBSac in acetonitrile or an acetone−water mixture produce the bromohydrin at room temperature (Scheme 499).1383 The reactions proceed with high anti stereoselectivity in short reaction time.

Scheme 503

was found to be an efficient bromine and nitrogen source for the aminobromination of β-methyl-β-nitrostyrenes with manganese(II) acetate as the catalyst in the presence of 4 Å molecular sieves. The reaction results in vicinal bromoaminonitroalkanes with the opposite regioselectivity compared with those reported, which was also confirmed by X-ray structural analysis. Paul et al. used TsNBr2 for the synthesis of 1-substituted 3,5dihydroxypiperidines from 1,4-pentadiene.1391 They achieved the synthesis via an intermediate methoxy bromide, which was synthesized by treating the reagent with olefin in methanol. However, the yield of the methoxy bromide was found to be very low. We have utilized this reagent for the synthesis of bromohydrins and alkoxy bromides from olefins (Scheme 504).1392 The method was very rapid and efficient, and no extra catalyst was required. The bromohydrin formation reaction was

Scheme 499

A procedure for the β-bromoformyloxylation of olefins with N,N-dibromobenzenesulfonamide (DBBS) and formic acid has been developed by Takemura.1384,1385 The synthesis was carried out by treating the olefin with 0.5 mol equiv of DBBS and 3 mol equiv of 99% formic acid in chloroform at low temperature. A similar cohalagenation of alkenes with DMF has been reported by de Souzafor for the synthesis of a vicinal bromoformyloxylated product using NBSac. The reaction of alkenes with NBSac in DMF followed by aqueous workup led to the corresponding β-bromoformate in high regio- and stereoselectivity (Scheme 500).1386 Kharasch and Priestley introduced N,N-dibromo-p-toluenesulfonamide as a reagent for the first time for the synthesis of 1-

Scheme 504

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performed by treating the olefin in a mixture of acetonitrile and water in a 4:1 ratio. Various olefins such as styrenes, cinnamates, acrylates, and cyclohaxene work very well to produce the corresponding bromohydrins instantaneously. Excellent yields and regio- and stereoselectivities have been obtained. All products are found to be anti-selective. The synthesis of alkoxy bromides was achieved by treating the olefin with TsNBr2 in anhydrous alcohol. The formation of alkoxy bromides takes 30−60 min at room temperature. Interestingly, when the reaction was performed in a mixture of tert-butyl alcohol and water, a mixture of tert-butoxy bromide and bromohydrin was obtained in a 1:3 ratio. We have also used this reagent for the synthesis of vicinal bromo azides. In this procedure, vicinal bromo azides were directly prepared from olefins using TsNBr2 without any catalyst in acetonitrile at room temperature (Scheme 505). We found that the reaction is

Scheme 507

in benzene in an autoclave at room temperature for 1 h pressurized with 30 atm of CO3. The method could be used in reactions with a wide range of olefins, both aromatic and aliphatic, as well as electron-rich and -deficient olefins, leading to the regioselective formation of aminobrominated compounds. Schmidt et al. studied the reaction of 2,4,4,6tetrabromocyclohexa-2, 5-dienone with cyclohexene and methanol and reported the formation of 1-bromo-2-methoxycyclohexane.1398 Tsubota and co-workers reported various reactions with alkenes in the presence of various bases. First, they synthesized (β-bromo-α-methoxyethyl)benzene from styrene in methanol (Scheme 508).1399

Scheme 505

Scheme 508

very fast, producing the corresponding bromo azides instantaneously in high yield. This procedure was applicable to various olefins such as cinnamates, chalcone, styrenes, and acrylate to give the corresponding 1,2-bromo azide in an excellent yield.1393 We have reported that formyloxy bromides and acetyloxy bromides can be formed instantaneously from olefins using TsNBr2.1394 The reaction was carried out by adding TsNBr2 to a solution of olefin in DMF or acetic acid under a nitrogen atmosphere at room temperature (Scheme 506). The one-step

They used this addition reaction to prepare some bifunctional adducts of cyclohexene in the presence of various bases (Scheme 509). Scheme 509

Scheme 506 Perbromides and N-bromo derivative of ε-caprolactum and of α-aminocaproic acid cyclooligoamides are versatile brominating agents. They were also reported as dehydrogenating agents. Korosi used N-bromo-ε-caprolactam for the hydrobromination of styrene to 2-bromo-1-phenylethanol (Scheme 510).1400

reaction goes very smoothly and instantaneously without any catalyst. All kinds of olefins such as styrene, cinnamate, acrylate, chalcone, and aliphatic olefins produce the corresponding product in excellent yield with high regio- and stereoselectivity. Using the same reagent, recently we have transformed alkynes to α,α-dibromo dimethyl ketals at room temperature in the presence of methanol. This catalyst-free protocol is instantaneous and very effective for aromatic and aliphatic alkynes.1395 With a binary solvent system such as CH3CN−MeOH (4:1) and THF−MeOH (4:1), the ketals were found to form with decreasing yield. A convenient and practical procedure for the aminobromination of electron-deficient olefins using bromamine-T as the nitrogen and bromine source promoted by diacetoxyiodobenzene was developed by Xia et al. This metal-free protocol is highly efficient and affords the vicinal bromamines with excellent stereoselectivities.1396 The reaction was carried out by heating the olefin with bromamine-T and PhI(OAc)2 in dichloromethane at reflux temperature for the appropriate time to give the aminobromine in high yield (Scheme 507). Hayakawa et al. developed a method for the CO2-induced amidobromination of olefins with bromamine-T.1397 The reactions were carried out with olefins using bromoamine-T

Scheme 510

Corey et al. carried out bromoamidation with Nbromoacetamide as the bromine source. They carried out the reaction with an olefinic substrate in acetonitrile in the presence SnCl4 as the activating Lewis acid (Scheme 511).1401 The substrate scope of the bromoamidation reaction is quite broad. Scheme 511

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Qi et al. reported the unexpected syn β-amino-α-bromination of unsaturated phosphonates under typical Sharpless asymmetric aminohydroxylation reaction conditions with excess Nbromoacetamide (NBA).1402 In this synthetic procedure, to a solution of vinyl phosphonate and (DHQ) 2 PHAL or (DHQD)2PHAL ligand in acetonitrile were added LiOH· H2O, potassium osmate dihydrate, and NBA to afford the aminobromination product (Scheme 512).

Zwierzak et al. prepared tert-butyl N,N-dibromocarbamate (BBC) easily by bromination of tert-butyl carbamate in aqueous potassium carbonate (Scheme 515).1407

Scheme 512

This reagent reacts smoothly with a variety of terminal alkenes to afford the corresponding β-bromo-N-Boc-amines upon reduction with aqueous sodium sulfite. Immediate deprotection of N-Boc-amines with gaseous HCl yields βbromo amine hydrochlorides in good yields (Scheme 516).

NBA has also been utilized for the synthesis of bromohydrins in regio- and stereoselective fashion from various olefins in the presence of N-tosyl-L-threonine (NTsLT) as an acidic additive.1403 The reaction was carried out using 1.2 equiv of NBA and 1 equiv of NTsLT in a 1:1 tert-butyl alcohol−water mixture at room temperature. The reaction provided bromohydroxylation products with α-hydroxy-β-bromo regioselectivity and exclusive anti selectivity. Pattisonet al. reported1404 the synthesis of aliphatic vicinal fluoro bromides by using N-bromoacetamide in anhydrous hydrogen fluoride and a number of aliphatic alkenes. The reaction was carried out at low temperature depending upon the nature of the alkene. Predominant formation of Markonikovs products was observed under the reaction conditions. Negero and Ikeda carried out the bromochlorination of styrene derivatives with tetrabutylammonium dichlorobromate as the bromine source in acetic acid or methanol in a regiospecific manner (Scheme 513). The reactions of 1phenylpropenes with this reagent produced nonstereospecific but regiospecific adducts.1405

Scheme 516

Scheme 515

The same group again described the addition of BBC to several straight and branched chain terminal alkenes, namely, styrene, 2-phenylpropene, isobutylene, 2-methylbut-1-ene, 3methylbut-1-ene, pent-1ene, hex-1-ene, hept-1-ene, oct-1-ene, and 2,4,4-trimethylpent-1-ene.1408 All reactions were carried out in refluxing dichloromethane by adding dropwise the solution of BBC to an equimolar amount of the alkene. They observed that the addition of BBC to styrene was disturbed by relatively fast consecutive cyclization of the primarily formed N-Boc-(2-bromo-2-phenylethyl)amine to 5-phenyloxazolidin-2-one (Scheme 517). This reaction was not observed for other alkenes.

Scheme 513

Scheme 517

In 1971, Robinson explored the possibility of using N,Ndibromobenzenesulfonamide (dibromoamine-B) to brominate norbornene, and a mixture of products was formed (Scheme 518).1409 One product is essentially the bromo compound, and the other is the aminobrominated product.

Zawadzki et al. described a two-step aminobromination of phenylethylenes and α-olefins with diethyl N,N-dibromophosphoroamidate (DBPA).1406 The reaction was found to proceed in boiling dichloromethane. It was found that the reaction is spontaneous or photolytically initiated depending on the structure and reactivity of the reactants. N-Bromo adducts, formed upon addition, could be reduced in situ with sodium bisulfite solution to give the corresponding diethyl N-(βbromoalkyl)phosphoroamidates. Degradation of the latter with hydrogen chloride in benzene at room temperature afforded βbromoamine hydrochlorides in the pure state and reasonable overall yield (Scheme 514).

Scheme 518

A facile regio- and chemoselective bromomethoxylation of alkenes under microwave irradiation conditions employing a polymer-supported bromine chloride resin was reported (Scheme 519). 1410 The resin was prepared from the commercially available chloride resin by a simple one-step procedure. Hiyama1411 developed a method for halofluorination of alkenes using DBH and tetrabutylammonium dihydrogen trifluoride in dichloromethane as the solvent at low temper-

Scheme 514

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Scheme 519

Scheme 522

ature. The method was regioselective as well as chemoselective. In a similar method, Walkowiak also used DBH as a source of electrophilic halogen in the presence of the 1,1,3,3,3pentafluoropropene−diethylamine (PFPDEA) complex as a fluoride source in halofluorination reactions of various olefins (Scheme 520).1412 The reaction was carried out in dichloro-

Lambeth et al. studied the oxidation of a variety of thioethers by bromine, including N-acetyl-DL-methionine, 5′-methylthioadenosine, and tetramethylene sulfide. The product of the oxidation of N-acetyl-DL-methionine was the corresponding sulfoxide. 1418 4,4′,6,6′-Tetraazidoazobis(1,3,5-triazine) (TAAT) was synthesized from 4,4′,6,6′-tetraazidohydrazobis(1,3,5-triazine) (TAHT) by the oxidative reaction with bromine and sodium hypochlorite (NaClO) with excellent yields (Scheme 523).1419

Scheme 520

Scheme 523 methane in the presence of hexamethylphosphoramide (HMPA) to produce the corresponding vicinal fluorobromides in high yield and regioselectivity. Arylacetylenes react with cyanogen bromide in dichloroethane in the presence of a catalytic amount of GaCl3 to afford (Z)-β-bromoacrylonitriles (Scheme 521).1413When the reaction

A method has been reported by Yuan and co-workers for obtaining a sulfoxide by oxidizing a thioether with air in the presence of liquid bromine in ethanol at room temperature.1420 In the microwave-assisted condensation of hydrazone derivatives with aldehydes, in an intermediate step, Br2/AcOH was used as the oxidizing agent. Here, the oxidation of 6-(4-chloro3-methylphenyl)-(2H)-4,5-dihydropyridazin-3-one with Br2 in acetic acid produced 6-(4-chloro-3-methylphenyl)-(2H)-pyridazin-3-one (Scheme 524).1421

Scheme 521

was carried out at 80 °C in the presence of 10 mol % GaCl3 for 12 h, the corresponding products were formed in a regioselective and stereoselective fashion as well as in high yield. The trihalide-based ionic liquid [bmin][IBr2]1414 has been used as a reagent as well as a solvent for the iodobromination of alkenes and alkynes, while the same can also be used as a reagent in another ionic liquid such as [bmin][PF6] as the solvent. The regioselectivity of the process depends on the nature of the ionic liquid as well as the structure of the substrate.

Scheme 524

In the process for the synthesis of statins by Casar et al., in one of the steps, chemoselective oxidation with bromine in water was conducted.1422 A spectrophotometric method for the determination of tannic acid in gallnut was described by Sun et al.1423 This method uses bromine for oxidizing the tannic acid, and the product was determined spectrophotometrically. Stereoselective intramolecular coupling of diaroylacetates of (1R,1′R)-exo,exo′-3,3′-biisoborneol was carried out by oxidation with bromine. Kise et al. adopted this process with a combination of sodium hydride and bromine to produce the corresponding intramolecularly coupled products stereoselectively (Scheme 525).1424 They also reported that the oxidative coupling of sodium enolates of (4R,5S)-1-(aroylacetyl)-3,4dimethyl-5-phenyl-2-imidazolidinones with bromine as the oxidant affords the R,R-dimers stereoselectively.1425

5. OXIDATION REACTIONS 5.1. Use of Molecular Bromine as an Oxidant

Liquid bromine has excellent oxidizing power. There are many examples found in the literature of oxidation reactions using this reagent. Bromine can oxidize long aliphatic and aromatic thiols to disulfides in solution in quantitative yield. Frost et al. used Br2 for the conversion of thiols to the corresponding disulfides.1415 A similar procedure was adopted by Wu et al. for the bromine-assisted conversion of thiols into disulfides.1416 Medium-length aliphatic disulfides were easily obtained in the absence of solvent. Ali et al. reported the oxidation of thiols to disulfides with Br2 on a silica gel solid support. The procedure uses dichloromethane as the medium of the reaction and does not require a base to neutralize HBr byproducts to suppress acid-promoted side reactions (Scheme 522). The use of a silica gel support simplifies the workup and product isolation.1417

Scheme 525

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Scheme 526

In an environmentally benign solventless system, alcohols were rapidly oxidized to carbonyl compounds using hexamethylenetetramine−bromine on wet Al2O3 under microwave irradiation.1426 Several 5-(arylimino)-2-phenyl-3-oxo-1,2,4-thiadiazolidines were prepared by oxidative debenzylation of 1-aryl5-phenyl-2-S-benzyl-2-isothiobiurets by bromine in a CHCl3 medium.1427 The required 1-aryl-5-phenyl-2-S-benzyl-2-isothiobiurets were prepared by the interaction of phenyl isocyanate and 1-aryl-S-benzylisothiocarbamide in a dry benzene medium. The oxidation reactions of [Li4{(NBut)3S}2] with O2 and Br2 were studied by Fleischer et al.1428 Stilbene was oxidized to benzil in 75−80% yield in 3−6 h with a solution of bromine in H2SO4 in boiling acetic acid.1429 Potentiostatic oxidation of the 1,2-bis(1,4-dithiafulven-6-yl)benzenes induces their intramolecular cyclization. Frere et al. described a method of oxidation of 1,2-bis(1,4-dithiafulven-6-yl)benzenes with bromine.1430 Oxidation of 1,9-bis(methylthio)dibenzothiophene with a combination of bromine, pyridine, l-menthol, and AgBF4 produced a sulfonium salt which on hydrolysis gave the corresponding sulfinyl compound.1431 In the synthesis of tetracyanohydroquinone, bromine was used as the oxidizing agent.1432 Kumar et al. used Br2 for oxidative bromination in the synthesis of 7azaindole derivatives.1433 Oxidative bromination of 7-azaindoles with bromine in 48% HBr in an aqueous medium resulted in the corresponding 3,3-dibromo-7-azaoxindoles and 3-bromo-7azaoxindoles (Scheme 526). The use of bromine water for the oxidation of dioxolane groups into esters in acetonitrile was achieved by Mingotaud et al.1434 The synthesis of various α-amino ketones via oxidation of the corresponding alcohols by bromine in anhydrous dichloromethane in the presence of Na2CO3 was described by Schinkowski.1435 For example, when (1S,2S)-1-(p-nitrophenyl)-2-acetamidopropane-1,3-diol was treated with bromine in boiling CH2Cl2 in the presence of anhydrous Na2CO3, the corresponding α-amino ketone was produced in 96% yield. The treatment of 3β-acetoxy-5α-cholestan-6-one with Br2 and HBr in a mixture of ether and acetic acid produced 1-methyl-19norcholesta-1,3,5(10)-trien-6-one, 5α-cholestane-3,6-dione, and 3β-acetoxy-5-bromo-5α-cholestan-6-one.1436 In the synthesis of 3-aryl-5-phenyl-1,4-dithiane 1,1-dioxides, 1,1,4-trioxides, and 1,1,4,4-tetroxides, bromine in pyridine and MeOH was used as the oxidizing agent.1437 Alcohols can be selectively oxidized by using bromine in the presence of organotin compounds.1438−1443 Tributyltin ethers1438,1439 and dibutyltin acetals1440,1441 prepared by using bis(tributyltin) oxide and bis(tributyltin) oxide, respectively, were oxidized to carbonyl compounds in the presence of molecular bromine. Bromine was used for oxidation in the preparation of crystals of the charge transfer complex of hexakis(alkylthio)benzene.1444 Tee et al. reported that formic acid is oxidized by bromine in aqueous solution, and the acidity dependence of the rate suggests that the reaction produces the bromide anion and carbon dioxide (Scheme 527).1445 They also reported that in the presence of α-cyclodextrin the rate of the reaction increases. α-Cyclodextrin modestly increases the rate of the reaction by forming a CD·Br3−

Scheme 527

complex. α,β-Epoxycycloalkanones were treated with 2.1 equiv of 2-lithio-2-(trimethylsilyl)-1,3-dithiane to give high yields of trans-2-dithianyl-3-dithianylidene-1-cycloalkanols, which were oxidatively hydrolyzed with an excess of bromine in alcohols to the corresponding acetal esters (Scheme 528).1446 Scheme 528

2-(Arylamino)-5-heteroaryl-6H-1,3,4-thiadiazines were prepared by Veerabhadraiah et al., where in the first step, oxidation of 3-acetylcoumarin arylthiosemicarbazones was carried out with bromine.1447 Oxidation of hydrazino-1,3,5-triazine with Br2 afforded bromohydroxytriazine and bromotriazine derivatives as products.1448 Several dimeric 1,2-bis(2,2′-bipyridinyl) ethane and 1,2-bis(1,10-phenanthrolinyl)ethane ligands have been synthesized in high yields by oxidative coupling of the corresponding monomeric methylene carbanions using Br2 as the oxidizing agent.1449 In the synthesis of cycloheptatrienes with sulfur functional groups, Br2 was used for oxidizing the substrate to the cyclic disulfide.1450 Imamura et al. studied the isomerization of pentane to isopentane over intermetallic compounds (LaAl2, CeAl2, PrAl2, ErAl2, SmAl, and ThAl2) oxidized with Br2. Increasing Br2 addition increases the activity of the catalyst, but the selectivity for isopentane decreases. Neither the intermetallics nor Br2 alone exhibited any catalytic activity.1451 N-(2-Oxoalkyl)acetamides were oxidized with Br2 at 20 °C in isopropyl alcohol or concentrated HCl to give butane-2,3-dione or 2-oxopropanal in high yield (Scheme 529).1452 Scheme 529

Bognar prepared monosaccharides from furfural derivatives.1453 Condensation of 2-furaldehyde with pinacol followed by oxidation of the product with bromine water and reduction with sodium borohydride produced DL-2-(1,4-dihydroxy-cisbut-2-enyl)-4,4,5,5-tetramethyl-1,3-dioxolane. Hydroxylation of the dibenzoate of this product followed by debenzoylation and hydrolysis produced DL-ribose and DL-arabinose. Deluzarche et al. studied the oxidation of secondary alcohols to cyclic ethers using the bromine−silver oxide reagent.1454 The oxidation by Br2−Ag2O of secondary alcohols with an active hydrogen on a 6934


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δ-C to tetrahydrofurans was quite sensitive to the solvent effect. For example, 3-heptanol in pentane produced a mixture of tetrahydro-2-propylfuran (20%) and 3-heptanone (61%). On the other hand, the same reaction in a mixture of pentane and 2,5-dimethyltetrahydrofuran as the solvent produced the respective products in the opposite ratio, with the formation of tetrahydro-2-propylfuran and 3-heptanone in 72% and 8% yields, respectively. Roscher and Jedziniak also studied the oxidation of alcohols by bromine and silver salt.1455 They found that the formation of cyclic ethers can be suppressed by the addition of an acid. For example, the presence of a strong acid during oxidation of 2-hexanol and menthol by Br2−silver trifluoroacetate lowered the formation of the tetrahydrofuran derivative and favored ketone production (Scheme 530).

The solvent-free oxidation of liquid o-xylene was carried out in the presence of a Co/Mn/Br2 catalyst in 85−92% yields to give phthalic acid.1463 Cyclohexene derivatives can be aromatized using bromine in carbon tetrachloride to produce the corresponding benzene derivatives in 70−80% yield.1464 Samoshin et al. carried out the brominative aromatization of 2alkylthio(arylthio)cyclohexanones to give 2-alkylthio(arylthio) phenols.1465 Treatment of 2-alkylthio(arylthio)cyclohexanones with bromine produced 2-alkylthio(arylthio)phenols (Scheme 533). Scheme 533

Scheme 530 4-Bromo-1-(bromomethyl)-2-(4-chlorophenyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile was synthesized by Huang et al. from 2-(4-chlorophenyl)-1-methyl-5-(trifluoromethyl)-2-pyrroline-3-carbonitrile by dehydrogenation with bromine in carbon tetrachloride and bromination of the pyrrole ring with bromine in carbon tetrachloride in the presence of Fe powder. This was followed by the photochemical bromination of CH3 group with NBS in CCl4 (Scheme 534).1466

Epoxidation of steroidal alkenes using bromine in the presence of Ag2O in a mixture of water and dioxane was found to be the preferred method for the formation of βepoxides.1456 The oxidation reaction using bromine with tropocollagen was studied under different conditions by Michlik.1457 The physical and chemical changes occurring in tropocollagen were mentioned. The amino acid composition, except tyrosine and proline, of the peptides released from these reactions is similar to that observed with the tropocollagen− pepsin system. Cox et al. studied the oxidation of aldehydes with bromine. Base-catalyzed oxidation by bromine of formaldehyde, acetaldehyde, and isobutyraldehyde led to the formation of the corresponding carboxylic acids.1458 Bis(methylsulfonyl) disulfide was prepared by the reaction shown in Scheme 531 in dry Et2O by Foss.1459

Scheme 534

Scheme 531 5.2. Application of NBS to Oxidation Reactions

N-Bromosuccinimide has been used as a very good oxidizing agent for various transformations. 4-Cholestene-3β,6β-diol was oxidized with NBS mainly to 3,6-cholestanedione, presumably through the intermediate formation of 4-cholestan-6β-ol-3-one. However, the yield was found to be 17%.1467 4β-Hydroxycholesterol was transformed to 3-keto-4β,5α,6β-trihydroxycholesterol using NBS under solid-phase conditions.1468 Dunstan and Henbest studied the course of the dehydrogenation of tertiary amines with NBS. They found that the reaction is efficient and produces the corresponding aldehydes and secondary amines in good yield.1469 The reaction of NBS with imidazole or with a number of its 4(5)-substituted derivatives, in aqueous media, leads to the oxidative degradation of the heterocyclic ring.1470 The products formed are ammonia, glyoxal, and formamide. From studies of the rate of consumption of oxidant, it is concluded that, as a result of intramolecular carboxyl participation, a labile lactone is formed as an intermediate in the oxidation of imidazole-4(5)-propionic acid and its analogues. Cyclic acetals were oxidized under mild conditions by NBS in the presence of AIBN to brominecontaining esters (Scheme 535).1471 An interesting feature of this reaction is that when carbon tetrachloride was used as the reaction medium, chlorine was found incorporated into the ester in place of bromine. Ketones,

Isbell studied the oxidation of aldoses with bromine water.1460 The introduction of BaCO3 into athe solution removes any free acid formed. During the course of the oxidation, aldoses are converted directly to the lactone. Aldehydic sugars can be oxidized by bromine. This method can be used for distinguishing aldehydic sugars from their ketonic counterparts since bromine oxidizes the aldehydic sugar only.1461 The time required to carry out this particular oxidation reaction is very long, with only 50% glucose being oxidized after 5 days. However, by addition of glacial acetic acid, the reaction time can be shortened to 24 h. A series of 3,4diaryl-2,5-dibromothiophenes were synthesized by a one-pot reaction of 3,4-diaryl-2,5- dihydrothiophenes with bromine in excellent yield (83−92%).1462 It was found that bromine performed a double function (oxidation and bromination) during the conversion of 3,4-diaryl-2,5-dihydrothiophenes to 3,4-diaryl-2,5-dibromothiophenes. (Scheme 532). Scheme 532

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in cis-3,3,5-trimethylcyclohexanol by NBS in aqueous dioxane. NBS acts as a suitable oxidant in DMSO.1482−1484 A one-pot synthesis of vicinal di- and triketones from α-methylene ketones by selective NBS−DMSO oxidation was investigated by Yasuji etal.1482 For example, with NBS in DMSO at ambient temperature, 1,2-diarylethanones produced the corresponding 1,2-diarylethanediones in 81−97% yield. 4-Phenyl-2-butanone, 1,3-diphenyl-2- propanone, and 1,3-diphenyl-1,3-propanedione produced the corresponding triketone monohydrates. Salomies carried out the oxidation of adrenergic β-receptor blocking agents sotalol and bupranolol with NBS.1485 Sotalol was oxidized in alkaline conditions, whereas oxidation of bupranolol was carried out in acidic reaction conditions. A rapid synthetic method of diarylcarbazone (ArNNCONHNHAr) from arylsubstituted carbazide was reported by Li et al.1486 It was prepared by the oxidation of aryl-substituted carbazide using NBS and pyridine as the oxidation system in good yield under mild conditions. This method needs only a short reaction time. NBS is also a very good oxidant in a water medium.1487,1488 A simple, one-pot, mild, and highly efficient biomimetic oxidation of various alcohols and epoxides with NBS catalyzed by βcyclodextrin in water has been developed by Krishnaveni et al.1487 They oxidized a series of alcohols and epoxides selectively at room temperature in excellent yields. NBS with neutral alumina is a good oxidizing system. A simple protocol for microwave-assisted solvent-free oxidation of hydrobenzoins to benzoins or benzils, benzoins to benzils, and alcohols to the corresponding aldehydes or ketones was reported by Khurana et al.1489 They observed that hydrobenzoin was selectively oxidized to give benzoin when exposed to microwaves for 20 s using 2 equiv of NBS and 3 equiv of neutral Al2O3 (Scheme 538). When the reaction was exposed to microwaves for 2 min,

Scheme 535

when heated with NBS in CCl4 in the presence of pyridine, produced the diketone.1472 The reaction can also be carried out in aqueous dioxane at room temperature to produce diketones with a better yield. When NBS was treated with N,N′dicyclohexylthiourea in the presence of pyridine, formation of dicyclohexylcarbodiimide and N,N′-dicyclohexylurea was found (Scheme 536).1473 Scheme 536

Oxidation of β-stannyl hydrazones with NBS gave azocyclopropanes in high yields.1474 Francis found that the oxidation of salicylic hydrazide with NBS in alkaline conditions produces salicylic acid.1475 He also established that the reaction proceeds via the formation of sodium hypobromite at an intermediate stage.1476 An oxidative esterification method has been developed on the basis of the reactivity of (trialkylstannyl) alkoxides toward NBS.1477 Treatment of tributylalkoxystannane (Bu3SnOCH2R) with 1 equiv of NBS in CCl4 produced the corresponding aldehyde (RCHO) or ester (RCO2CH3) in good yield. Oxidation of silyl ethers RCHMeOSiMe3 (R = Ph, n-hexyl) with NBS under UV irradiation provides the ketones RCOMe in 55−76% yields (Scheme 537).1478 A similar

Scheme 538

Scheme 537

it produced benzil in quantitative yield. Other hydrobenzoins, namely, p,p′-dichlorohydrobenzoin and o,o′-dichlorohydrobenzoin, could also be oxidized selectively under these reaction conditions. Oxidation of benzyl alcohol and other secondary alcohols can be achieved using an equimolar mixture of NBS and Bu4NI in acetonitrile at room temperature.1490 This procedure selectively produces benzaldehyde from benzyl alcohol. A method for converting 1,2,3,5,6,10b-hexahydropyrrolo[2,1-a]isoquinolines into 5,6-dihydropyrrolo[2,1-a]isoquinolines by the use of NBS as an oxidant was presented by Nyerges et al.1491 The same group also reported another method for converting 1,2,3,5,6,10b-hexahydropyrrolo[2,1-a]isoquinolines into 5,6dihydropyrrolo[2,1-a]isoquinolines using NBS as an oxidant (Scheme 539).1491 Uzagare et al. described a method for the oxidation of nucleoside phosphite triester into phosphate triester under

oxidation of silyl ethers Me(CH2)5OSiMe3 and PhCH2OSiMe3 produced Me(CH2)4CO2(CH2)5Me and benzaldehyde, respectively. Irradiation of various silyl ethers in the presence of aldehydes and NBS gave mixed esters. For example, irradiation of a mixture of decanal with ethoxytrimethylsilane and NBS produced Me(CH2)8CO2Et. The environment of tryptophan residues of the γ-subunit derived from the 7S nerve growth factor has been studied for oxidation with NBS along with intrinsic fluorescence and solute quenching. NBS (20−24 mol of NBS/mol of protein) completely oxidized one tryptophan of the γ-subunit.1479 The liquid-phase oxidation of toluene was carried out in the presence of NBS and Co(OAc)2 in methanol under pressure. When the reaction was carried out in the presence of Co(OAc)2 and NBS, benzoic acid was obtained selectively, while, with NBS alone, benzaldehyde was the main product. The oxidation proceeds by a radical mechanism.1480 The oxidation of cyclohexanol by NBS was performed by Chung and Kim.1481 The axial hydroxyl in trans-3,3,5-trimethylcyclohexanol was oxidized more readily than the equatorial hydroxyl

Scheme 539

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nonbasic and nonaqueous conditions using NBS−DMSO in CH3CN.1492Selective oxidations of the exo cyclic double bond of spiroacetal enol ethers with multiple reactive sites can be achieved using NBS in the presence of AgNO3 for the synthesis of spiropyanones.1493 Benzylic C−H bond oxidation has been achieved using NBS.1494,1495 Mayhoub et al. carried out an oxidation of benzyl methyl ethers with NBS that selectively affords either aromatic aldehydes or aromatic methyl esters.1494 By controlling the amount of NBS and the temperature, one can obtain either mono- or dibromination of benzyl methyl ethers. Then elimination of methyl bromide from the monobrominated intermediates produces aromatic aldehydes, whereas hydrolysis of the dibrominated intermediates gives aromatic methyl esters in good yields (Scheme 540).

Scheme 542

initial step involves NBS-mediated oxidation of the hydroxyl group.1499 Sain et al. reported the use of cobalt(II) acetylacetonate as the catalyst for the oxidation of secondary alcohols to carbonyl compounds with NBS.1500 A variety of activated and unactivated secondary alcohols were selectively oxidized to the ketones using the cobalt(II) catalyst in acetonitrile at reflux temperature (Scheme 543).

Scheme 540

Scheme 543

The method of oxidizing alcohols with air in the presence of 0.2 mol % TEMPO, 4−10 mol % NBS, and 4−10 mol % sodium nitrite in a mixture of water and dichloromethane as the reaction medium at 100 °C was developed by Liu et al.1501 Fan et al. reported the oxidation of aliphatic and aromatic alcohols to their corresponding aldehydes and ketones with Nbromosuccinimide.1502 The reaction was carried out with alcohol in polyethylene glycol using NBS at temperature of 60 °C. Jain and Sain reported that the oxidizing property of NBS can be enhanced significantly by the addition of NH4Cl to the reaction medium.1503 They achieved the oxidation of a variety of benzylic and secondary alcohols in excellent yields using NBS in combination with NH4Cl in aqueous acetonitrile at 80 °C. NBS also behaves as a good oxidant in an ionic liquid.1504,1505 Lee et al. found a procedure for the oxidation of benzylic alcohols to carbonyl compounds using NBS in an ionic liquid.1504 They carried out the oxidation reaction using NBS in the presence of 2,6-lutidine in (bmim)BF4 ionic liquid. The use of a mixture of water and dioxane can promote the oxidizing action of NBS without any catalyst.1506 Adimurthy showed that benzylic alcohols can be converted selectively to the corresponding aldehydes using NBS in a mixture of H2O and dioxane as the reaction medium. Hanessian and Roy developed a convenient procedure for the selective oxidation of a secondary alcohol of a sugar derivative using a combination of (Bu3Sn)2O and NBS.1507 They effected preferential oxidation of a 4(R)-hydroxyl group in the presence of a pair of axially (C7) and equatorially (C-9) disposed hydroxyl groups (Scheme 544) during the synthesis of spectinomycinan antibiotic. The procedure involved the initial treatment of the sugar derivative with bis(tri-n-butyltin) oxide in benzene followed by NBS. A similar transformation of dibutylstannylene acetals derived from 1,2-diols was reported by Kong and Grindley.1508 They found that the regioselective oxidation of a seconday alcohol in the presence of a primary one can be achieved by treating the corresponding stannylene acetal with NBS in chloroform. When the reaction is carried out with the acetal derived from terminal diols, it leads to exclusive formation of the ketol instead of the hydroxy aldehyde. A method for the amidation of the benzylic sp3 C−H bond was developed using NBS as the oxidant in the presence of

Under open-flask conditions, the synthesis of a series of diversely functionalized diaryl ketones from the corresponding diarylmethanes has been carried out in the presence of NBS by Xiong et al.1495 They observed that the addition of stoichiometric water with CHCl3 as the solvent and under reflux conditions eventually leads to excellent yields. Stuckwisch developed a procedure for the oxidation of aliphatic secondary alcohols with NBS under anhydrous conditions.1496 Secondary alcohols can be selectively oxidized in the presence of a primary alcohol using NBS.1497,1498 Corey established that one can selectively oxidize secondary alcohols in the presence of primary alcohols using NBS in aqueous dimethoxyethane.1497 The reaction was carried out by exposing the diol to 1.5 equiv of NBS in 10% aqueous dimethoxyethane at 25 °C for 1 h (Scheme 541). Scheme 541

Tripathi and Mukherjee also reported a similar method of selective oxidation of secondary alcohols with NBS.1498 They used thiourea derivatives as a catalyst for this reaction. The reaction was carried out in dichloromethane at 0 °C for about 36 h, which could promote the chemoselective oxidation of secondary alcohols in the presence of primary alcohols (Scheme 542). Sekar et al. synthesized α-amino ketones from benzylic secondary alcohols using NBS in dioxane at room temperature. The reaction proceeds via three consecutive steps where the 6937


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Scheme 544

FeCl2 as the catalyst.1509 For example, treatment of ethylbenzene with benzamide and NBS and a catalytic amount of FeCl2 in ethyl acetate at 50 °C produced the corresponding N(1-phenylethyl)benzamides in 68% yield (Scheme 545).

Scheme 547

Scheme 545

intermediate bromosulfonium salt to the product, allowing the reaction to employ a nonaqueous medium. Ghafuri et al. reported a method for the preparation of symmetrical aliphatic, aromatic, and heteroaromatic disulfides with the help of NBS (Scheme 548). The reaction was carried out under catalyst-free conditions in dichloromethane to produce the corresponding disulfides in nearly quantitative yields.1518

Liang et al. developed a very effective NBS−DBU system1510−1513 to achieve the amination of ketones, Nsubstituted indoles, and α,β-unsaturated carbonyl compounds (Scheme 546). DBU activates NBS to achieve a more electrophilic bromine and a more nucleophilic nitrogen atom. In the presence of an external amine, allylic amination can be achieved.1512


Lorance et al. prepared dithiins using NBS.1519 For this, they reacted (Z,Z)-1,4-bis(tert-butylthio)-1,4-bis(trifluoromethyl)1,3-butadiene and (Z,Z)-1,4-bis(tert-butylthio)-1,4-bis(pentafluoroethyl)-1,3-butadiene in CH3CN under red light to give 3,6-bis(trifluoromethyl)-1,2-dithiin and 3,6-bis(pentafluoroethyl)-1,2-dithiin (Scheme 549). Scheme 549

Dhiman et al. reported the use of polymer-supported NBS as an oxidizing agent.1514 They prepared poly(ethylene-g-Nbromosuccinimide) (PE-g-NBS) through the graft copolymerization of maleic anhydride (MAn) onto polyethylene (PE) by a photochemical method with 1% benzophenone as a photosensitizer. The polymer-supported NBS was used successfully for the oxidation of a series of alcohols, including 2-propanol, 1-butanol, ethylene glycol, cyclohexanol, poly(vinyl alcohol), benzoin, benzyl alcohol, and chloromycetin, to their corresponding aldehydes and ketones. Equimolar amounts of NBS and aromatic sulfides, stirred in 70% dioxane−H2O, gave the corresponding sulfoxides.1515 Harville also introduced a method for the oxidation of sulfides to sulfoxides.1516 The oxidation of sulfides was carried out in anhydrous methanol employing NBS at a temperature of 0−5 °C. An efficient and highly selective procedure for the oxidation of sulfides to sulfoxides with NBS in the presence of hydrated silica gel was developed by Ali et al. (Scheme 547).1517 Hydrated silica gel supplies the water necessary for the decomposition of the

Bajpai et al. developed a method for the oxidation of substituted pyrrolidines with NBS which leads to the formation of 3,4-disubstituted maleimides.1520 NBS was also found to be suitable for the oxidation of fused 1,4-dimethoxybenzenes1521 and naphthalene derivatives1522 to produce the corresponding benzoquinones. The oxidative demethylation of 5,8-dimethoxy2-methylquinoline using 1.1 equiv of NBS in aqueous THF and a catalytic amount of H2SO4 at 20 °C for 5 min gave 2methylquinoline-5,8-dione in 98% yield without bromination (Scheme 550).1522 Oxidation of indoles to isatins has also been accomplished using NBS. The reaction is thought to proceed via a 3,3dibromooxindole as an intermediate.1523 The reaction was carried out with a mixture of 1-alkyl-7-azaindole, NBS, and anhydrous DMSO at 60 °C for 6 h, and then the reaction was 6938


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Scheme 550

Scheme 554

continued above 80 °C for 20 h under reduced pressure (Scheme 551).

water to give the corresponding α-amino ketones in high yields. They proposed that β-cyclodextrin forms inclusion complexes of the aziridines and water can attack only at the exposed αposition of the aziridine in the supramolecular complex, which is facilitated through hydrogen bonding with β-CD to form α,βhydroxyamine, which is oxidized by NBS to yield α-amino ketones (Scheme 555).1530

Scheme 551

Scheme 555 Fuchs and Funk have isolated and used 3-alkyl-3bromooxindole as a key intermediate in the elegant syntheses of (±)-flustramines A and C.1524 In this case, 3-alkyl-6bromoindole was treated with NBS in a mixture of tert-butyl alcohol, THF, and water to afford the key 3-alkyl-3-bromo-6bromoindolin-2-one (Scheme 552).

Surendra et al. described a method for the oxidation of sulfides to sulfoxides with NBS in the presence of βcyclodextrin in water. They reported a series of sulfides which were oxidized selectively at room temperature in excellent yields. This reaction went without overoxidation to sulfones (Scheme 556).1531

Scheme 552

Scheme 556

Tian et al. developed a procedure for the conversion of a 1methyl-1H-indole derivative to the corresponding 1-methylindolin-2-one derivative via an NBS-assisted oxidative transformation.1525 They adopted a two-step procedure involving sequential C-2 bromination and hydrolysis to obtain the oxindole derivative (Scheme 553). This procedure was applied to achieve the total synthesis of (−)-N-methylwelwitindolinone C isothiocyanate.1526

Surendra et al. used the cerium(IV) ammonium nitrate and NBS combination to oxidize epoxides and aziridines. The oxidized products were α-hydroxy ketones and α-amino ketones from oxiranes and aziridines, respectively, in excellent yields. This was a direct synthesis under mild conditions using acetonitrile−water (9:1) as the solvent (Scheme 557).1532


Wang et al. proposed a method for the direct oxidation of Nbenzylamides to aldehydes or ketones by NBS.1527 The method is a simple, efficient, and one-pot transformation and produces the corresponding aldehydes in moderate to excellent oxidative yields. The efficacy of NBS as an oxidant during the asymmetric oxidation of 1,2-diol has been investigated.1528,1529 Onomura et al. investigated the asymmetric oxidation of 1,2-diols using NBS in the presence of copper(II) triflate and (R,R)-Ph-BOX. This oxidation was applicable for the asymmetric desymmetrization of meso-hydrobenzoin and the kinetic resolution of dlhydrobenzoin and racemic cycloalkane-cis-1,2-diols to afford optically active α-keto alcohols with good to high enantiomeric excess (Scheme 554).1528 Reddy et al. used NBS for the oxidative cleavage of arylaziridines involving β-cyclodextrin−aziridine complexes in

Meyers et al. introduced a method for the oxidation of oxazolines to 1,3-oxazoles using NBS.1533 The reactions were carried out by treating 2-aryl-2-oxazoline with NBS and AIBN in carbon tetrachloride to give the 5-bromo-1,3-oxazoles in 50% yield (Scheme 558). Another method for the synthesis of oxazoles was developed by Fujioka et al. using NBS as the oxidant.1534 They used a Scheme 558

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mixture of NBS with K2CO3 for oxidation of 3-oxazoline to oxazoles in dichloroethane under relux conditions. The oxazoles were obtained with a high yield. The synthesis of furan-3-carboxylic acid and derivatives was carried out by Zanatta et al. from the aromatization of 4-(trichloroacetyl)-2,3dihydrofuran with NBS in CCl4 under reflux conditions (Scheme 559).1535 This was followed by nucleophilic displacement of the trichloromethyl group by hydroxide, alcohols, and amines to form the corresponding acid, esters, or amide in high yield.

Scheme 562

catalyst can also effect the 3-bromination of oxindoles by NBS, but in neutral aqueous t-BuOH, 5-bromooxindoles are formed. In glacial AcOH, NBS effects bromination of the indole hetero ring. Symmetrically hindered 4-methylphenols react smoothly with NBS to form transient intermediates, i.e., p-benzoquinone methides (BMs), which can be further processed to give hydroxybenzaldehydes in the presence of DMSO.1542 This reaction is initiated by the formation of the phenoxy radical, followed by disproportionation to afford BMs. None of the side-chain-brominated product is observed (Scheme 563).

Scheme 559

Again, NBS helps the oxidation of 5-aminopyrazoles to give bisdiazenyl derivatives. Treatment of 5-amino-4-cyanopyrazoles with NBS in DMF at room temperature gave azo dyes resulting from dimerization through the amino groups and further oxidation.1536 Majetich and co-workers introduced a method for the synthesis of epoxide from olefins using NBS in DMSO and subsequent addition of DBU. They successfully synthesized epoxides from aliphatic as well as aromatic substrates.1537 Shibasaki adopted a similar strategy for the epoxidation of a tetrahydroindolizin-5(3H)-one derivative to achieve the total synthesis of (+)-lentiginosine (Scheme 560).1538 In their method, the precursor olefin was treated with NBS in a mixture of THF, ether, and water followed by dehydrobromination using potassium carbonate in methanol.

Scheme 563

Gauna et al. synthesized alkyl 4,5-dibromo-2-methylbenzoate derivatives from 1,2-dibromo-4-(alkoxymethyl)-5-methylbenzene in the presence of NBS as a radical initiator.1543 When a mixture of substrate (1 equiv) and NBS (1 equiv) was heated overnight under reflux in carbon tetrachloride, esters were obtained in good yields (Scheme 564).

Scheme 560

Scheme 564

Schwekendiek et al. described a new methodology for the synthesis of variously substituted 2-oxazolines and one dihydrooxazine using aldehydes and amino alcohols and in the presence of NBS as an oxidizing agent in dichloromethane (Scheme 561). This synthesis was carried out under mild reaction conditions with a broad substrate scope and high yields.1539,1540

A simple and convenient procedure has been developed for the synthesis of benzils and aliphatic 1,2-diketones of cyclic and open chain compounds from the corresponding hydrobenzoins and 1,2-diols by refluxing with NBS in carbon tetrachloride in the presence or absence of pyridine (Scheme 565).1544 In a typical experiment, NBS and pyridine were used as an oxidnation system to dehydrogenate aryl-substituted semicarbazide or carbazide to form azo compounds in one phase.1545 The yields of the products were excellent under mild conditions. A reaction of NBS with benzyl ethers (CH2Ph, Bu, Et, 2,4,6-Br3C6H2, Ph) and phenyl ethers (MeOC6H4,

Scheme 561

NBS in tert-butyl alcohol converts 3-alkylindoles such as skatole, indole-3-acetic acid, and other indole-3-alkanoic acids into the corresponding oxindoles when a 1:1 mole ratio of NBS to indole is used.1541 The use of a 2:1 ratio of reactants resulted in the formation of 3-bromooxindoles in high yield (Scheme 562). However, bromination of the intermediate oxindoles was not observed in dry conditions as NBS does not attack oxindoles in dry alcohol. However, in the presence of moisture, HBr formed in the reaction catalyzes the bromination reaction to produce the corresponding 3-bromooxindoles, probably by way of the enol form of the oxindole. The presence of a base

Scheme 565

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PhCH2) in CCl4 in the presence of benzoyl peroxide or under ultraviolet radiation was examined. Benzyl ethers gave the corresponding benzaldehydes in favorable yields. The bromination of phenyl ethers occurs at the para or ortho position.1546 Kobayashi et al. reported that 2-substituted furans were conveniently transformed into trans-4-oxo 2-enals by using NBS in the presence of pyridine in a mixture of THF, acetone, and water as the reaction medium (Scheme 566).1547 The

Scheme 569

Scheme 566 An enantioselective synthesis of γ-nitro esters by asymmetric Michael addition/oxidative esterification of α,β-unsaturated aldehydes was presented by Jensen et al.1552 The procedure was based on merging the enantioselective organocatalytic nitroalkane addition with an NBS-based oxidation. The γ-nitro esters are obtained in good yields and enantioselectivities, and the method provides an attractive entry to optically active γamino esters, 2-piperidones, and 2-pyrrolidones. They performed the Michael reaction between aldehyde and nitromethane by applying 10 mol % (S)-2-[diphenyl[(trimethylsilyl)oxy]methyl]pyrrolidine as the catalyst in methanol at room temperature. Under these conditions, full and clean conversion to the Michael adduct was observed. The oxidative esterification was then achieved by the addition of 1.5 equiv of NBS, and full conversion to the desired methyl ester was observed (Scheme 570). The product was obtained in 58% yield and 94% ee.

initial addition of the reagent was carried out at −15 °C followed by the reaction at room temperature. This reaction also works well with a combination of NBS and NaHCO3 in a mixed medium of acetone and water. Again, a method for converting 2H-furfuryl alcohols to 2Hpyran-3(6H)-ones by the use of NBS as an oxidant was presented by Georgiadis et al. (Scheme 567).1548 The reactions Scheme 567

Scheme 570

were carried out with 1 equiv of furfuryl alcohol dissolved in a mixture of THF and water in a 4:1 ratio at 0 °C. They also selectively oxidized 2-furfuryl alcohol derivatives in the presence of aryl thioethers. NBS selectively oxidizes the furfuryl alcohols without affecting the thioether substituents. In the one-pot synthesis of pyranones, catalytic asymmetric alkylation of 2-furfurals in the presence of catalytic amino alcohol (−)-MIB generates enantioenriched furyl zinc alkoxides, which on subsequent treatment with a mixture of water and THF followed by NBS result in the formation of pyranones with >90% ee’s and yields between 46% and 77%.1549 In this case, NBS acts as an oxidizing agent to promote the formation of the desired pyranones (Scheme 568).

Furans can be oxidized to the corresponding butyrolactone using NBS as the oxidant.1553,1554 Martin et al. has synthesized 2,5-dialkoxy-2,5-dihydrofuran from 3-substituted furans1553 via NBS-assisted oxidation, followed by alcoholysis. A similar oxidation process of compounds containing the furan substructure has already been reported by Gopalakrishnan et al.1554 They established a procedure for the oxidation of tetranortriterpenoids from Azadirachta indica A. Juss and Soymida febrifuga (Meliaceae) using NBS.1554 The reaction proceeds to completion in 1 min on being subjected to microwave irradiation. However, the reaction takes 48 h for completion at 0 °C. In all these cases, the furan moiety present in these limonoids undergoes a partial oxidation, leading to a butyrolactone (Scheme 571). Ketones possessing an α-hydrogen undergo smooth thiocyanation with ammonium thiocyanate in the presence of

Scheme 568

During the study of the reaction between aldehydes and NBS, it was observed that p-nitrobenzaldehyde under CO2, treated with ammonia and water, provides a mixture of pnitrobenzamide and p-nitrobenzoic acid.1550 Various aldehydes could be transformed under this reaction condition, except for o-nitrobenzaldehyde, 5-bromovanillin, and 5-nitrovanillin, which failed to give any acid or amide. An efficient one-pot procedure for the cyanoimidation of aldehydes was developed by Yinet al. in the absence of a catalyst to form the corresponding key intermediate N-cyano imidates using NBS as an oxidant.1551 The reaction was carried out at 50 °C after initial addition of the reagent at room temperature. Subsequent reaction of the N-cyano imidates with phenylhydrazine produced the 5-alkyl-2-phenyl-2H-1,2,4-triazol-3-amine in high yield (Scheme 569).

Scheme 571

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NBS at room temperature in acetonitrile under neutral conditions to produce the corresponding α-keto thiocyanates in excellent yields with high selectivity.1555 In this reaction, NBS was used as an oxidant to obtain the final α-keto thiocyanates (Scheme 572).

Scheme 575

Scheme 572

solution,1564 oxidation of digol,1565−1567 oxidation of amino acids and peptides,1568−1573 oxidation of various sugars,1574−1579 and oxidation of different acids1580−1584 such as ethylenediaminetetraacetic acid,1580,1583 aspartic acid,1581 malic acid,1582 and citric acid1584 were reported. Similar studies were undertaken for the oxidation of allyl alcohol,1585−1587 benzyl ethers, 1588 benzhydrols, 1589 amines and amino alcohols,1590−1594 glycols,1595,1596 cardiotoxin II,1597nitrones and N,α-diphenylnitrones,1598,1599 dibenzyl sulfoxide,1600 and substituted aromatic acetals.1601 Oxidative cleavage of thiamine hydrochloride1602and phenylpropanolamine1603 and oxidative conversion of glutathione to glutathione disulfide,1604 were also studied in a similar context. During the study of the oxidation of azides with NBS, it was observed that the rate of oxidation of N3− in an aqueous medium is proportional to [N3−] and [NBS] at constant [Hg(OAc)2].1605 NBS has been used as an oxidizing agent in various flow injection chemiluminescence methods for the determination of cationic surfactants,1606 meloxicam,1607 urea,1608 sulfide,1609 prednisone acetate,1610 and timolol maleate1611 and the spectrophotometric determination of famotidine,1612 catecholamine,1613 and other drug molecules.1614 A method for the synthesis of unsymmetrical and symmetrical thiosulfonates was developed by Huayue1615 through NBS-promoted sulfenylation of sulfinates with disulfides. The process exhibits broad functional group tolerance (Scheme 576). Phenyl methoxymethyl sulfides undergo oxidative conversion to the corresponding phenylmethanesulfinate on treatment with NBS in methanol in 53− 98% yield.1616

1556

has demonstrated a new approach for the Sun et al. oxidative kinetic resolution of secondary alcohols using the Mn(III)−salen complex as the catalyst and NBS as the oxidant. The reaction was carried out using 1 mol % Mn(III)−salen in a 1:2 mixture of DCM and water at room temperature. Fujioka et al. prepared imidazolines in a one-pot operation from aldehydes and diamines through the oxidation of aminal intermediates by NBS (Scheme 573).1557−1561 This method could be applied to Scheme 573

various aromatic and aliphatic aldehydes and 1,2-diamines at room temperature. The reaction proceeds through a bromination−dehydrobromination process and is chemoselective. In the synthesis of 7-substituted benzolactam-V8’s, Ma et al. used NBS for the aromatization reaction.1562 Condensation of L-valine benzyl ester toluenesulfonic acid salt with a substituted cyclohexadione followed by aromatization with the help of NBS provided an N-aryl L-valine benzyl ester (Scheme 574). This intermediate was converted into 7-substituted benzolactamV8’s using an asymmetric Strecker reaction. Scheme 574

Scheme 576

Another important NBS-promoted reaction is oxidative coupling of β-keto esters.1563 Here, NBS with potassium tertbutoxide helps in the formation of a C−C single bond and a CC double bond. An interesting feature of this process is that addition of 2.1 equiv of NBS and tert-BuOK results in a C−C single bond, whereas formation of a CC double bond can be achieved by using 5 equiv of NBS and tert-BuOK (Scheme 575). Many kinetic and mechanistic studies were carried out by different researchers for different oxidation reactions by using NBS as the oxidizing agent. For example, kinetic and mechanistic studies on the oxidation of cycloheptanol in acid

Again, direct oxidative coupling of styrenes with aldehydes was described by Sudalai et al. for the synthesis of α,β-epoxy ketones using NBS/DBU/DMSO as an oxidative system at ambient conditions.1617 Feng1618 reported a process for the oxidative amidation of benzylic C−H bonds by using a Au(III) catalyst in the presence of NBS as the oxidant. They used sulfonamide and carboxamide as the nitrogen sources (Scheme 577). The reaction was carried out by treating the benzylic reagent (2 equiv) with amide (1 equiv) and NBS (1 equiv) in acetonitrile in the presence of the Au−bipy complex (3 mol %) at 70 °C. 6942


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carbonate (Scheme 580). The reaction proceeds via the formation of bromohydrin, and the addition of base generates

Scheme 577

Scheme 580

5.3. Oxidation Reactions Using Other Bromo-Organic Compounds

the epoxide. This one-pot procedure can be utilized for the stereoselective synthesis of epoxides from cinnamic esters in excellent yield in a shorter reaction time with exclusive formation of the trans isomer. The method was further extended successfully to styrenes. Kajigaeshi et al. used benzyltrimethylammonium tribromide for the oxidation of alcohols and ethers. The reaction was carried out using benzyltrimethylammonium tribromide in carbon tetrachloride in the presence of aqueous Na2HPO4 and sodium acetate at 60−70 °C. The reaction of primary alcohols or simple ethers and α,ω-diols or cyclic ethers with this system gave dimeric esters and lactones, respectively. The secondary alcohols in the presence of buffer at 60 °C gave ketones.1631 It was reported that pyridinium bromochromate is a good oxidizing agent for all kinds of alcohols to the corresponding carbonyl compounds. The synthetic utility of this reagent was increased in the presence of glacial acetic acid.1632 Quinolinium bromochromate (QBC) has also been used as an oxidant for all kinds of alcohols. Pandurangan investigated the oxidizing property of QBC and found that primary and secondary alcohols could be converted to the corresponding aldehydes or ketones in 71−94% yield on treatment in acetic acid for 2−8 h.1633 Floyd et al. reported the reaction of acetophenones with aqueous hydrobromic acid (HBr) in dimethyl sulfoxide, which led to the formation of arylglyoxals in good yield (Scheme 581).1634 All reactions were carried out at 55 °C with the reactant in the presence of HBr in an aqueous medium.

The oxidizing property of N-bromoacetamide is well-known in the literature.1619−1621 Singh and co-workers carried out kinetic and mechanistic studies of oxidation reactions using Nbromoacetamide as the oxidizing agent in the presence of various metal catalysts.1622,1623 Ghammamy et al. synthesized two reagents, namely, tetrapropylammonium bromochromate(VI), [N(Pr)4]CrO3Br, and tetrabutylammonium bromochromate(VI), [N(Bu)4]CrO3Br. They have utilized these reagents for the oxidation of a number of organic substrates in dichloromethane at room temperature with a quantitative yield (Scheme 578).1624 Scheme 578

We have reported the use of N,N-dibromo-p-toluenesulfonamide (TsNBr2) as an efficient reagent for the oxidation of alcohols.1625 This reagent can be prepared by treating an aqueous solution of chloramine-T with bromine.1626 The use of 1 equiv of TsNBr2 is enough to promote complete oxidation without any catalyst in acetonitrile as the reaction medium. This procedure works well at room temperature and is applicable to different kinds of primary and secondary alcohols, such as aromatic, aliphatic, cyclic, and benzylic alcohols to give the corresponding carbonyl compounds in excellent yield (Scheme 579). The remarkable feature of this reagent is that it

Scheme 581

Scheme 579

Tetraethylammonium bromochromate (TEABC), tetrahexylammonium bromochromate (THexABC), and tetraheptylammonium bromochromate (THepABC) were the reagents used for almost quantitative conversion of alcohols into the corresponding aldehydes and ketones by Ghammamy et al. (Scheme 582).1635 These reagents are very effective for nearly quantitative oxidation of alcohols under mild and acid-free conditions. The polymeric DABCO−bromine complex was used to convert primary and secondary alcohols to the corresponding aldehydes and ketones.1636 The reaction was carried out in a

oxidizes primary alcohols very efficiently in excellent yields besides other secondary and benzylic alcohols, which undergo oxidation within a short time. Primary benzyl alcohol is converted to both the aldehyde and acid simultaneously, whereas aliphatic primary alcohol is converted to the aldehyde only. Using this reagent in the presence of a weak base, alcohols and aldehydes can be subjected to an esterification process.1627 Similar results were reported by Ghosh et al.1628 from aldehydes using NBS; however, the method was limited by the scope of the substrates. Py·HBr3 reagent has also been reported in such an esterification process.1629 We have developed a method for the synthesis of epoxide from cinnamic esters without any catalyst.1630 The reaction was performed in a mixture of acetonitrile and water in a 4:1 ratio using TsNBr2 at room temperature followed by the addition of potassium

Scheme 582

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biphasic system consisting of dichloromethane and water at room temperature. A variety of 1,2-diols were selectively oxidized to their corresponding 1,2-diketones with bromamineT using RuCl3·xH2O as the catalyst in an alkaline mixture of acetonitrile and water in a 1:1 ratio. The reaction was pH dependent (pH 8.4), and at higher pH the rate of the reaction decreased significantly.1637 [Bmim][Br3] can also be used for the oxidation of alcohols into aldehydes and ketones in mild conditions and good yields.1638 Tribromoisocyanuric acid (TBCA) can be used for the oxidation of thiols to the corresponding disulfides in dichloromethane.1639 It is an effective oxidizing agent for the synthesis of disulfides under mild and heterogeneous conditions at room temperature with good to excellent yields (Scheme 583).

Scheme 585

the use of N-1,2-ethanediylbis(p-toluenesulfonamide) (BNBTS),1647 poly(N,N′-dibromobenzene-1,3-disulfonamide1,2-ethanediyl),1648 and N,N,N′,N′-tetrabromobenzene-1,3-disulfonamide1649 for the same reaction. The oxidation of 1,3,5-trisubstituted 4,5-dihydro-1H-pyrazoles and -isoxazoles to their corresponding aromatic derivatives could be achieved using the bisbromine−1,4diazabicyclo[2.2.2]octane complex (DABCO−Br2) in acetic acid at room temperature. The desired 2-pyrazoles and isoxazoles were produced in yields of 87−95% and 78−95%, respectively.1650 DBH has also been used for the oxidation of mono- and bisurazoles to their corresponding triazolinediones in excellent yield. In this case also, the use of a solvent such as dichloromethane was found to be beneficial in increasing the product yield compared to the solvent-free process (Scheme 586).1651

Scheme 583

Another method for the oxidative coupling of thiols to their corresponding disulfides was presented by Ghorbani-Vaghei et al. using poly(N-bromobenzene-1,3-disulfonamide) (PBBS), N,N,N′,N′-tetrabromobenzene-1,3-disulfonamide (TBBDA), and the DABCO−bromine complex. The reaction was applicable to a variety of thiols with high chemoselectivity.1640 Bromodimethylsulfonium bromide was also able to oxidize thiol in dichloromethane in the presence of triethylamine to give a 96% yield of the disulfide.1154 Singh et al. studied the kinetics and mechanism of the oxidation of valine by Nbromophthalimide in the presence of the chloro complex of Pd(II) as a homogeneous catalyst.1641 The oxidation of Lleucine by NBP was reported by Katre. They studied the effect of the cationic surfactant cetyltrimethylammonium bromide (CTAB) on the oxidation of L-leucine by N-bromophthalimide (NBP) at 308 K.1642 3-Bromo-4,4-dimethyl-2-oxazolidinone (NBDMO) was prepared, and its oxidizing property was compared to that of NBS. A procedure for the oxidation of sulfide to the corresponding sulfoxides was reported by Chaudhuri et al. using cetyltrimethylammonium tribromide (CTMATB) as the oxidant (Scheme 584).1643 They carried out

Scheme 586

Later, it was found that N,N,N′,N′-tetrabromobenzene-1,3disulfonamide (TBBDA) is also an effective oxidizing agent for the conversion of urazoles and bisurazoles to the corresponding triazolinediones under heterogeneous conditions at room temperature with good to excellent yields (Scheme 587).1652 Scheme 587

Scheme 584

the reaction in a mixture of acetonitrle and water at room temperature in the presence of 1 equiv of the reagent to produce the desired sulfoxide in high yield. 1,3-Dibromo-5,5-dimethylhydantoin (DBH) has been used as an oxidizing agent for the oxidation of 1,3,5-trisubstituted pyrazolines to their corresponding pyrazoles under both heterogeneous and solvent-free conditions.1644 Azarifar and his co-workers studied the oxidation of different kinds of 1,3,5trisubstituted pyrazolines in the presence of DBH in CCl4 or solvent-free conditions at room temperature (Scheme 585). The use of carbon tetrachloride was found to be beneficial in increasing the yield of the corresponding pyrazoles. They also showed that the reaction time can be significantly shortened by carrying out the reaction in the presence of silica gel under microwave irradiation.1645 This reagent was also used for the above reaction under microwave irradiation with a catalytic amount of mesoporous SiO2.1646 The same group also reported

Khazaei et al. used DBH as a suitable oxidant for the oxidation of thiols1653 and alcohols.1654 They oxidized thiols to disulfides within a very short reaction time in excellent yield at room temperature.1653 When they compared the activity of the reagent in dichloromethane and the solid phase using 1−1.5 equiv of the oxidant, the solvent-free condition was found to be more effective in accelerating the reaction rate, and the reaction was complete in 1−10 min with an excellent yield. However, Alam found that the use of 0.20−0.25 mol equiv of DBH is enough in oxidizing thiols in chloroform at room temperature to achieve an excellent yield of the corresponding disulfide.1655 Stannylene derivatives of monosaccharides were successfully oxidized to their hydroxy ketones by using DBH in chloroform. The reaction is very fast and high yielding.1656 The reaction was found to be extremely fast and produced no other oxidized side products. The silica-supported 1,1,3,3-tetramethylguanidine− 6944


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Br2 complex can be used in the heterogeneous phase in water for selective oxidation of aliphatic and aromatic sulfides to the corresponding sulfoxides and oxidative coupling of thiols to disulfides in a short reaction time.1657 A number of sulfides were readily oxidized with the bromine complex of 1,4diazabicyclo[2.2.2]octane in 70% aqueous acetic acid to furnish the corresponding sulfoxides in good yield.1658 GhorbaniChoghamarani et al. oxidized a wide range of aliphatic or aromatic sulfides selectively to the corresponding sulfoxides using 1,2-dipyridinium ditribromide−ethane in a biphasic mixture of CH2Cl2 and water under heterogeneous conditions in moderate to high yields.1659 NBSac has successfully been used for the chemoselective oxidation of thiols to their corresponding disulfides in dichloromathane under microwave irradiation in high yield.1660The same group also reported that oxidative coupling of thiols can be achieved using N-1,2ethanediylbis(p-toluenesulfonamide) for the production of the corresponding disulfides at room temperature with good to excellent yields.1661 Khazaei et al. prepared 1-bromo-5,5diethylbarbituric acid and 1,3-dibromo-5,5-diethylbarbituric

Scheme 589

Scheme 590

590).1666 Bromoethyl ketones were formed in high yield when alkynes were treated with the gold catalyst (5 mol %) in the presence of methanesulfonic acid and 8-methylquinoline Noxide in dibromoethane as the solvent at room temperature. The conversion of benzyl trimethylsilyl ether to benzaldehyde in the presence of both the bromodiethylbarbituric acids was conducted in different solvents. The results showed that the efficiency and the yield of the reaction in dichloromethane were better than in other solvents (Scheme 591). It is noteworthy that tetrahydropyranyl (THP) ethers remained

Scheme 588

Scheme 591 acid (Scheme 588) by brominating the corresponding 5,5diethylbarbituric acid in the presence of a base. They have utilized these bromo compounds for the oxidative cleavage of different kinds of trimethylsilyl ethers in good yields at room temperature.1662 1,2-Dibromoethane was utilized as a suitable reagent for the oxidative coupling of benzyl anions.1663,1664 In this process, benzylic metalation of substituted toluenes was carried out using BuLi/KO-t-Bu/TMP(H) at the initial stage followed by C−C coupling in the presence of 1,2-dibromoethane as the oxidant. Using this protocol, m-xylenes were metalated regioselectively at the benylic position to provide a dimer, which on subsequent in situ benzylic metalation and oxidative

intact under these reaction conditions, which facilitate the selective oxidation of trimethylsilyl (TMS) ethers. Benzyltriphenylphosphonium tribromide (BTPTB) was also able to promote a similar oxidation reaction of trimethylsilyl ethers to their corresponding carbonyl compounds in a mixture of methanol and water in high yields.1667 Symmetric 2,2′dimethoxy-10,10′-biacridinyl-9,9′-dione atropisomers were obtained by the oxidative coupling of 9(10H)-acridinone with 1,3Scheme 592

Figure 3. [2.2]Metacyclophane.

coupling with 1,2-dibromoethane produced [2.2]metacyclophane (Figure 3) in high yields. 1,2-Dibromoethane has also been utilized as an oxidant for carbonylative homocoupling of arylzinc compounds in the presence of the Rh−dppf catalyst.1665 Symmetrical diaryl ketones are obtained in good yield using this process in the presence of CO (1 atm) in THF at 60 °C (Scheme 589). The process is also effective in the presence of Pd and Ni compounds; however, the Rh catalyst was found to be more effective for this reaction. α- Oxo gold carbenes generated via gold-catalyzed intermolecular oxidation of terminal alkynes were found to be highly electrophilic toward 1,2-dibromoethane (Scheme

dibromo-5,5-dimethyl-imidazolidine-2,4-dione (Scheme 592).1668 Bromamine-T is a good oxidant which can be prepared by treating an aqueous solution of chloramine-T trihydrate with bromine at room temperature followed by the addition of aqueous NaOH to the precipitate of dibromamine-T.1669 A variety of tertiary amines were efficiently and selectively oxidized to the corresponding N-oxides by bromamine-T using ruthenium trichloride as the catalyst at 80 °C (Scheme 593).1670 The reaction was highly dependent on the pH of the reaction. The best condition was pH 8.4. The solvent system was a mixture of acetonitrile and water in a 1:1 ratio. 6945


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Scheme 593

Scheme 596

bromine in methylene chloride at room temperature to afford the desired product (Scheme 596). Regioselective bromination of 3,4-dihydro-2-pyridones at the methyl group was accomplished with bromine in acetic acid. The corresponding dibromides underwent thermal heterocyclization to the 4-aryl-3-cyano-1,2,5,7-tetrahydrofuro[3,4-b]pyridine-2,5-diones.1679 Koren et al. synthesized thiadiazolopyridines by using bromine in acetic acid.1680 2,3-Dihydro-3methoxyfuro[2,3-b]quinolines were prepared by the addition of 3-vinyl-2-quinolones to methanol−bromine followed by cyclodehydrobromination of the resulting methoxy bromide.1681 The bromination of 2-hydroxydibenzoylmethanes using dioxane− bromine gave bromoflavones in 60−70% yields.1682 Feng et al. reported a method for producing 3-methyl-2(3H)-benzothiazolinone hydrazone. Here, in one of the steps involved, Nmethyl-N-phenylthiourea was allowed to react with bromine in chloroform under refluxing conditions for 45−60 min to obtain 2(3H)-imino-3-methylbenzothiazole.1683 Electrophilic addition of bromine to N-acyl-2-(2-alkenyl)anilines was accompanied by intramolecular cyclization of these amides to give 3,1benzoxazine hydrochlorides or hydrobromides in high yields.1684 Substituted 2-bromomethyl-2,3-dihydrobenzofurans were synthesized in one pot and in mild yield from substituted o-allylphenols with diacetoxyiodobenzene in the presence of bromine in dry CH2Cl2 under reflux.1685 The reaction of Nacetyl-2-(cyclohex-1-enyl)aniline with bromine in carbon tetrachloride at 20 °C produced spirobenzoxazine, whereas bromination of the cyclopentenylacetanilide with bromine in carbon tetrachloride produced diastereomeric (dibromocyclopentyl)acetanilides.1686 In the synthesis of 2,1-benzoxaselenol3-one, Lambert carried out the sequential treatment of (methylseleno)nitrobenzoic acid with bromine in the presence of pyridine in dichloromethane to produce a 75% yield of benzoxaselenolone.1687 Fujisawa reported that the key step for the jasmone synthesis is the cyclization of 4,5-dibromopentan2-one with a base. For this they carried out the bromination of 4-methyl-3-pentyl-4-penten-2-one with bromine in dichloromethane at −15 °C followed by treatment with 2 N sodium

Bromamine-T oxidizes isoniazid and glutathione stoichiometrically in a pH 5 acetate buffer medium with four- and tenelectron changes, respectively.1671 Rangaswamy et al. carried out the oxidation of glutamic acid and its rare earth complexes with bromamine-T. The oxidation of ML3·3H2O (LH = glutamic acid; M = Y, La, Pr, Nd, Sm, Gd, Tb, Dy, and Ho) with bromamine-T was completed in 5 min with a 12-electron change per complex molecule in pH 4 acetate buffer.1672 Our group successfully utilized bromamine-T as a source of nitrogen for the Sharpless asymmetric aminohydroxylation (AA) reaction of alkenes. It has been introduced as a new nitrogen source for the AA process, and the method is very effective in terms of yield and reaction time of the process. The method is highly regioselective, and β-amino alcohols are obtained with moderate to high optical purities.1673 Quaternary ammonium bromate was prepared from the corresponding bromide and Scheme 594

used as an oxidizing agent for the aromatization of Hantzsch esters and related compounds to pyridine derivatives (Scheme 594).1674 A convenient and practical method for the one-pot synthesis of ω-bromo esters from aromatic aldehydes and diols in the Scheme 595

presence of pyridinium hydrobromide perbromide as the brominating reagent and triethoxymethane as the dehydrating agent was developed by Aoyama et al. (Scheme 595).1675 The reactions were carried out in dichloromethane as the reaction medium at 50 °C. A series of aromatic aldehydes were used for this reaction. Among monobromobenzaldehydes, the order of reactivity was p-bromobenzaldehyde → m-bromobenzaldehyde → o-bromobenzaldehyde; the ortho isomer is less reactive than the para and meta isomers.

Scheme 597

hdroxide at 55 °C for 16 h to produce dihydrojasmone in 61% yield (Scheme 597).1688 Similarly, bromolactonization can be achieved by treating γ,δunsaturated acids with molecular bromine. Corey developed a procedure for the bromolactonization reaction by treating the olefin with bromine in dichloromethane in the presence of Tl2CO3.1689 A similar method was also adopted by Cambie and co-workers for halolactonizations of γ,δ-unsaturated acids.1690 Treatment of 2-isopropenylcyclopropylphosphonates and -phosphinates with bromine resulted in cyclization to give oxaphosphabicyclo[3.1.0]hexanones.1691 Martin et al. established that the addition products of benzimidazoline-2-thione and isocyanates are easily cyclized to benzimidazolothiadiazo-

6. CYCLIZATION REACTIONS 6.1. Use of Molecular Bromine for Cyclization Reactions

Bromocyclization of aminomethyl ethers of allyl and propargyl alcohols were performed by reaction with molecular bromine to oxazolidinium bromides.1676 Imidazoles were prepared by cyclizing substituted N-allylpseudothiohydantoins and Nallylpseudothiohydantoic acids with bromine and potassium acetate.1677 1-Aza-4-cyclooctene reacted with bromine to give pyrrolizidines by stereospecific transannular cyclization.1678 The reaction was carried out with 1-aza-4-cyclooctene using 6946


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room temperature. Bromine reacts within 10 min or less to afford the product. This strategy has been extended for the synthesis of 2,3-disubstituted benzo[b]furans by electrophilic cyclization of 1-methoxy-2-(1-alkynyl)benzene in the presence of bromine.1703 Aryl-, and vinyl-substituted alkynes undergo electrophilic cyclization in excellent yields. Further extension of the reaction could lead to a pathway for 2,3-disubstituted benzo[b]selenophenes from the corresponding 1-(1-alkynyl)-2-(methylseleno)arenes in the presence of bromine as the cyclizing agent in dichloromethane (Scheme 601).1704 This method tolerates a wide variety of functional groups, including alcohol, ester, nitrile, nitro, and silyl groups, and proceeds with a high yield.

Scheme 598

line systems by treatment with bromine (Scheme 598).1692 The reactions were carried out with bromine in the presence of triethylamine in chloroform as the reaction medium. Pyridinecarbonitriles were prepared by the cyclization of 2(3-chloro-5,5-bis(methylthio)pent-4-en-2-ylidene)malononitrile ((NC)2CCRCClC(SMe)2) with bromine.1693 Rajendra and Millar found that the oxidative cyclization of unsaturated hydroxamates with bromine−K2CO3 produces βlactams.1694 They carried out the reaction by treatment of hydroxamates with bromine in the presence of potassium carbonate in a mixture of acetonitrile and water initially at 0 °C to room temperature (Scheme 599).

Scheme 601

Scheme 599

Manarin and co-workers also reported a similar strategy to accomplish the synthesis of 3-substituted 2-chalcogenobenzo[b]furan compounds via the electrophilic cyclization reaction of 2-(chalcogenoalkynyl)anisoles using Br2 as one electrophile source (Scheme 602).1705

In the cyclocondensation reaction of ethyl 2-aryl-2butenoates with cinnamates, bromine in CS2 and in pyridine was used as the dehydrogenating agent.1695 Aroyl(benzothiazolyl)thioureas were obtained by the reaction of 2-aminobenzothiazoles with aroyl isothiocyanates, which underwent cyclization by bromine in acetic acid or chloroform to give (aroylimino)benzothiazolothiadiazolines in 48−62% yield.1696 In the preparation of 3-(arylimino)-5-[2-(6-methyl)benzothiazolyl]imino-1,2,4-dithiazolidines, Br2 was used for the cyclization reaction in CHCl3 as the reaction medium.1697 6-(5-Aryl-2furyl)-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazoles were prepared by intramolecular cyclization of the (furfurylideneamino)triazoles with thionyl chloride or bromine in acetic acid.1698 The synthesis of 5-(arylimino)-2-(p-tolylsulfonyl)-3-oxo-1,2,4-thiadiazolidines was achieved by oxidative debenzylation and cyclization with Br2 in moistened CHCl3 of the corresponding biurets, TsNHHCONHC(SCH2Ph) = NC6H4R, in moderate yields.1699 In the synthesis of pyridothienopyridines and arylazothienopyridines, Moneam et al. used bromine in acetic acid or ethyl chloroacetate for the cyclization of thiourea to afford thiazolothienopyridine.1700 3-Amino-5-(substituted amino)-1,2,4-thiadiazoles and 3-(substituted thiocarbamido)5-(substituted amino)-1,2,4-thiadiazoles were prepared by the oxidative heterocyclization of (thiocarbamoyl)guanidines and 1,3-bis(thiocarbamoyl)guanidines, respectively, with molecular bromine.1701 2,3-Disubstituted benzo[b]thiophenes are readily prepared in excellent yields by the Pd/Cu-catalyzed crosscoupling of o-iodothioanisole and terminal alkynes, followed by electrophilic cyclization by bromine (Scheme 600).1702 The cyclization reaction was carried out by treating the methyl(2-(1alkynyl)phenyl)sulfane with bromine in dichloromethane at

Scheme 602

A wide variety of substituted naphthalenes are readily prepared regioselectively under mild reaction conditions by electrophilic cyclization of the appropriate arene-containing propargylic alcohols by bromine as one of the cyclizing agents.1706 The products were formed in good yield when bromine was treated with the substrate in acetonitrile at room temperature in the presence of NaHCO3 (Scheme 603). Scheme 603

Pyrido[3,2-d]pyrimidines (R2N = piperidino, 1-pyrrolidinyl) were prepared by Eisa et al., where bromine was used for the oxidative cyclization of the intermediate hydrazones in acetic acid.1707 Courtneidge et al. studied the intramolecular cyclization of simple allylic hydroperoxides to give substituted 1,2-dioxolanes using the electrophilic reagent Br2.1708 The reactions were carried out using 1 equiv of bromine in icecooled solutions of CDCl3 (Scheme 604). Transannular cyclization of spiro[7-methylene-3,2-bicyclo[3.3.1]nonane-1,3-dioxolane] was carried in the presence of bromine.1709 Fagan generated a procedure for the conversion of 2-pyrazolines to the corresponding pyrazoles by treating the substrate with bromine at a temperature of 80 °C.1710

Scheme 600

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Scheme 604

Scheme 607

D’hooghe et al. synthesized 3,3-dialkyl-5-(bromomethyl)-1pyrrolinium bromides via bromocyclization of N-(2,2-dialkyl-4pentenylidene)amines.1711 The reaction was carried out by treating the corresponding N-(2,2-dialkyl-4- pentenylidene) amines with molecular bromine in dichloromethane at 0 °C. The reaction is very fast and runs to completion in 15 min to produce the desired product in high yield (Scheme 605).

Yu et al. proposed that a multicomponent reaction of 2alkynylbenzaldehyde, sulfonohydrazide, bromine, and ketone or aldehyde under mild conditions proceeds smoothly to afford the functionalized H-pyrazolo[5,1-a]isoquinolines in good yields (Scheme 608).1719

Scheme 605

Scheme 608

Treatment of (p-hydroxyaryl)propan-2-one oximes with bromine or NBS facilitates intramolecular cyclization to produce the corresponding 2,5-dienone spiroisoxazolines in high yield.1712 The regiochemistry of halocyclization reactions for olefinic and acetylenic sulfides was examined by Ren et al.1713 Thus, benzyl((E)-4-alkylbut-3-enyl)sulfanes, PhCH2S(CH2)2CHCHR (R = H, Et, Ph), were treated with bromine in dichloromethane and 3-chloroperbenzoic acid to give bromotetrahydrothiophene dioxides in 90−95% yield. Sevenmembered cyclic sulfides (R = H, Ph) were exclusively produced by treating PhCH2S(CH2)4CHCHR with 1 equiv of Br2 in CH2Cl2, which produced PhCH2S(CH2)4CHBrCHBrR. In the synthesis of bicyclopropylidenes in the intermediate step, Br2 was used for the bromination of cyclopropylcyclopropanol.1714 Reaction of 2′-amido-m-terphenyl with NaOH and Br2 gave the substituted phenanthridinone. Thermolysis of 2′-azido-m-terphenyl also gave the phenanthridinone in good yield. The synthesis of 2′-m-terphenyls was accomplished via Suzuki coupling.1715 A wide variety of substituted naphthalenes were prepared regioselectively under mild reaction conditions by the 6-endo-dig electrophilic cyclization of the appropriate arene-containing propargylic alcohols by bromine as one of the reagents (Scheme 606).1716

6.2. Use of NBS in Cyclization Reactions

Sakurai and co-workers reported a method for the synthesis of 1β-methylcarbapenems using NBS-promoted cyclization as a key step. NBS-promoted cyclization of α-ethoxy enoates afforded functionalized 1β-methylcarbapenams, which were subsequently converted to 1β-methylcarbapenem, in a stereospecific manner.1720 The reaction was carried out by adding NBS to a solution of substrate in acetonitrile at 20 °C (Scheme 609). Scheme 609

Reaction of 1,4-butanediol or 1,5-pentanediol with NBS produces γ-butyrolactone or δ-valerolactone, respectively, in high yields.1721 Bicyclo[3.2.0]hept-3-en-6-ones undergo a tandem fragmentation−cyclization to the corresponding unsaturated lactones by reaction with NBS in an aqueous medium.1722 The reactions were carried out with the substrate in a mixture of DME and water at 0 °C (Scheme 610). With 4-

Scheme 606

Scheme 610

unsubstituted reactants the halohydrins are the intermediates in this process and are heated to provide the lactones. In the case of 4-methyl-substituted bicycloketones, the procedure proved to be an effective chemo- and regiospecific method for the preparation of the corresponding lactones. A similar strategy was adopted by Tsubuki and co-workers for the enantiocontrolled synthesis of (−)-swainsonine.1723,1724 Hajra used NBS for the synthesis of 1,5-disubstituted tetrazoles taking metal triflate as the catalyst in a one-pot reaction system using alkenes, nitriles, and (TMS)N3 at room

The cyclohalogenation reaction of 3-methyl-1,2,4-pentatriene-1-phosphonic acid esters with Br2 was studied by Angelov et al. The reaction of this compound gave two diastereoisomers.1717 The oxidative intermolecular cyclocondensation of 3,4-diaminofurazan and 4,4′-diamino-3,3′-azofurazan was carried out by treating them with mixtures of Pb(OAc)4 and Bu4NBr, Br2, or NaBr to give the previously unknown macrocyclic compounds polydiazenofurazans (Scheme 607).1718 6948


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temperature (Scheme 611).1725 Among the metal triflates, Zn(OTf)2 was found to be the best catalyst. The use of

diarylfurans with excellent regiocontrol and high yields (Scheme 617A).1733 Alkynyl-substituted arene carbonyl compounds undergo similar bromocyclization process in the presence of an external nucleuophile with NBS, and the protocols are very effective for preparing O-and N-heterocycles.1734,1735 Larock prepared highly substituted oxygen heterocycles by reacting o-(1alkynyl)-substituted arene carbonyl compounds with NBS and various alcohols or carbon-based nucleophiles.1734 The reactions were carried out at room temperature in the presence of 1.2 equiv of NBS and 1 equiv of potassium carbonate in dichloromethane (Scheme 617B). Ouyang et al. studied the CuI/I2-promoted electrophilic tandem cyclization of 2-ethynylbenzaldehydes with o-benzenediamines.1735 They synthesized haloisoquinoline-fused benzimidazoles using NBS (Scheme 618). Treatment of 2ethynylbenzaldehyde with o-benzenediamine and NBS in the presence of a catalytic amount of CuI in DMSO at 120 °C afforded the bromoisoquinoline-fused benzimidazoles in moderate yield after 24 h of reaction. Peng et al. has reported the bromocyclization of [2-(1alkynyl)phenyl]phosphonic acid diester and α-aryl-substituted alkynylphosphonic monoesters, providing the synthesis of phosphaisocoumarins and bromo enol phostones, respectively. The latter process is mediated by the presence of a suitable base (DMAP). In this process DMAP deprotonates or partially deprotonates the phosphonic monoester, enhancing the nucleophilicity of the phosphonyl group. It also stabilizes the bromonium ion intermediate during the process.1736,1737 Falck et al. reported the facile formation of bromo boronolactones via the exposure of (o-alkenylaryl)boronic acids to NBS in a mixture of THF and water as the reaction medium (Scheme 619).1738 Corey reported the bromolactamization of the N-Boc derivatives of unsaturated amides using NBS and lithium tertbutoxide in tetrahydrofuran.1739 High yields of the corresponding bromo N-Boc-α-lactams are obtained using this procedure. Mellegaard et al. used NBS for bromolactonization of unsaturated acids with NBS (Scheme 620).1740 The reaction was carried out using 1.1 equiv of NBS in acetonitrile at −30 °C for 2 h in the presence of diphenyl diselenide as the catalyst. Braddock et al. reported ortho-substituted iodobenzenecatalyzed bromolactonization reactions using NBS as the bromine source.1741 The reactions were carried out using a 10 mol % concentration of the catalyst and 1 equiv of NBS in CDCl3 at room temperature. NBS has also been successfully utilized in the asymmetric bromolactonization reaction.1742−1750 Zhang et al. carried out bifunctional-catalystpromoted highly enantioselective bromolactonization of (Z)enynes.1742 The reactions were carried out by taking the substrate in dichloroethane using NBS at room temperature for 5−10 h in the presence of a 20 mol % concentration of the catalyst. Yeung et al. discovered cinchona alkaloid-derived amino thiocarbamates as catalysts for the asymmetric bromolactonization of olefinic carboxylic acid and olefinic

Scheme 611

different combinations of alkenes and nitriles generates a variety of 1,5-disubstituted tetrazoles containing an additional α-bromo functionality of the N1-alkyl substituent. Yeung et al. have developed a highly efficient, novel one-pot synthesis of imidazoline using olefin, nitrile, amine, and Nbromosuccinimide (Scheme 612).1726 A wide range of imidazoline derivatives have been synthesized using a variety of olefins and nitriles. The reaction is initiated by the bromonium ion. The reaction is highly convenient as it proceeds under mild conditions without any external catalyst. Rezaie and Bremner synthesized some fused indole derivatives from lactam-containing m-cyclophanes in the presence of NBS.1727 They found that the treatment of lactam-containing m-cyclophanes with NBS led to fused indole derivatives via intramolecular cyclization. However, the reaction does not proceed with an N-protected lactam functionality in the bridging ring. NBS along with DBU promotes the cyclization of (N-alkylthioureido)indoles and alkyl N-(indol5′-yl)dithiocarbamates to furnish only the corresponding 2(alkylamino)- and 2- (alkylthio)thiazolo[5,4-e]indoles regioselectively (Scheme 613).1728 The reaction was carried out in dichloromethane at −10 °C to produce the thiazolo[5,4-e] indoles in high yield. A synthesis of the CDE ring system of tetrahydroisoquinoline antitumor alkaloids such as saframycins, renieramycins, and ecteinascidins was developed by Obika et al.1729 Here, NBSmediated oxidative Friedel−Crafts cyclization of the resulting 2ketopiperazine was utilized as a key reaction. Treatment of the precursor substrate 2-[(3-arylprop-2-ynyl)amino]-3-(2,4,5-trimethoxy-3-methylphenyl)propanamide with NBS in acetonitrile at 60 °C could produce the desired product in 15 min (Scheme 614). Winkler et al. reported the stereoselective aldol reaction of 3silyloxyfurans with aldehydes in the presence of a Lewis acid.1730 Here the NBS-mediated cyclization of the aldol product leads to the formation of the 2,7-dioxa-bicyclo[2.2.1] heptan-3-one ring system, which represents the formal product of the hetero-Diels−Alder reaction of the furan with the aldehyde (Scheme 615). In the synthesis of trioxadispiroketals, McDermott and coworkers1731 applied NBS to effect an oxidative tandem cyclization of two proximal hydroxyl groups onto a central furan core, allowing direct access to the [5,5,5]-trioxadispiroketal and the [6,5,6]-trioxadispiroketal ring systems (Scheme 616). Yoshizaki and co-workers synthesized 3-deoxy-D-manno-2octulosic acid (KDO) derivatives with the help of NBSpromoted deprotection of the dithioacetal group of the precursor molecule.1732 Sniady et al. carried out 5-endo-dig electrophilic cyclization of 1,4-diarylbut-3-yn-1-ones with NBS and acetone at room temperature in the absence of a base to give 3-halo-2,5-

Scheme 612

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Scheme 613

Scheme 618

tion of N-tosylcarbamate catalyzed by the chiral phosphine− Sc(OTf)3 complex.1755 Using this protocol, higly enantiopure oxazolidinones could be synthesized. A similar strategy has also been utilized by Ohfune and Kurokawa for the synthesis of 3(Boc-amino)-5-(bromomethyl)-dihydrofuran-2(3H)-one derivatives starting from the corresponding chiral allyl glycene precursor.1756−1758 Tang et al. developed a syn 1,4-bromolactonization process of enynic acids by using NBS in the presence of the DABCO catalyst.1759 The reaction was carried out using 1.2 equiv of NBS in the presence of 2 mol % DABCO in chloroform at room temperature. The method was found to be highly regioand diastereoselective. They further extended the process by

Scheme 614

Scheme 615


using cinchona urea catalysts for enantioselective bromolactonization of (Z)-1,3-enynes and 1,1-disubstituted olefins with NBS (Scheme 622).1750 The catalysts developed for this reaction are composed of a cinchona alkaloid skeleton attached to a substituted urea group. Snider and Johnston investigated the halolactonizations of γ,δ-unsaturated acids and found that the reaction using NBS in a mixture of THF and acetic acid or bromine in methanol

1743−1749

dicarbonyl compounds with NBS. The cinchona alkaloid-derived amino thiocarbamate offers a framework for catalyst modification controlling the selectivity. They reported the synthesis of γ-lactones from unsaturated olefinic acid.1743 The reaction was carried out with a 10 mol % concentration of the catalyst in the presence of NHNH2 as an additive (50 mol %) in a mixture of CHCl3 and toluene (1:2) at −78 °C. They also found NBS to be a better brominating source in comparison with N-bromophthalimide and 1,3-dibromo-5,5dimethylhydantoin in terms of yield and enantiomeric purity of the product. Using 1,2-disubstituted olefic acid with NBS in the presence of a catalytic amount of the amino thiocarbamate catalyst, they observed the formation of δ-lactones (6-endolactone) containing two chiral centers with up to 99% yield and 95% ee (Scheme 621).1744 By carrying out structural modification over the catalyst, they synthesized regioselective 5-exo-lactones from cis-1,2-disubstituted olefinic acid.1745 They

Scheme 620

produces a mixture of γ-lactone and δ-lactone.1760 There are a few other reagent combinations for the bromolactonization reaction using NBS, which include examples such as NBS/ AcOH−THF−H 2 O,1761,1762 NBS/DME−H 2O, 1763 NBS/ KHCO3/Bn4NOH/CH2Cl2−H2O,1764 and NBS/NH4PF6/ MeOH.1765 Yeung has shown another catalytic bromolactonization of long-chain olefinic acids using NBS using a zwitterionic catalyst.1766 This work resulted in an efficient synthetic route for medium-sized lactones. Similar asymmetric bromocyclization protocols were also developed using chiral phosphoric acids as the catalyst with NBS.1767,1768 Kumar et al.1769 found that isoselenazolones can be used as catalysts for the bromolactonization of alkenoic acids with bromine or NBS in the presence of potassium carbonate as a base (Scheme 623). They also utilized this catalytic system for the bromoesterification of a series of alkenes using NBS and a variety of carboxylic acids. Oxidation of secondary alcohols to ketones was also successfully carried out using the same procedure. Isoselenazolone(IV) dibromide is responsible for the activation of bromine under the reaction conditions.

Scheme 617

also reported enantioselective bromoaminocyclization1751−1755 leading to formation of pyrrolidines1751−1753 and piperidines1754 using similar amino thiocarbamate catalysts with NBS. Shi et al. reported a method for the bromoaminocycliza6950


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using 1.2 equiv of NBS in methylene chloride at room temperature. Nakoji reported Pd-catalyzed asymmetric allylic alkylation of glycine imino ester using a chiral phase transfer catalyst.1781 In

Zhao et al. used NBS in the presence of PPh3 to carry out chemoselective cyclodehydration of diols. 1,4-Diols and their derivatives can be rapidly cyclized to furnish tetrahydrofurans in high yields with 1 equiv of Ph3P/NBS. A higher amount of Ph3P/NBS leads to the formation of dibromobutanes.1770 McErlean has synthesized the furan framework in (+)-luzofuran via an electrophilic bromocylclization process.1771 Carbohydrates were selectively converted to 5-(hydroxymethyl)furfural

Scheme 623

Scheme 621

using NBS as the promoter.1772 Demole and Enggist developed a procedure for the synthesis of (Z)-4-methylcyclohept-4enones from a 3-methylhepta-1,6-dien-3-ol derivative by treating the corresponding diene with NBS in CCl4 under refluxing conditions followed by treatment with collidine under the same conditions.1773,1774 The same strategy was followed by Urones for the synthesis of 1-acetyl-3-α,6-dimethylhexahydroazulene starting from (±)-nerolidol.1775 In the conversion of homoallylic alcohols with alkene protection to the corresponding methyl ketones, Marquez carried out the cyclization of either the homoallylic alcohols or the corresponding benzyl ethers to the bromotetrahydrofurans (Scheme 624).1776 It is noteworthy that the treatment of the homoallylic alcohol with NBS in dichloromethane furnished only one diastereomer of the desired products. Praly and co-workers developed a procedure for the synthesis of oxathiazole derivatives using NBS as the promoter.1777 They found that the treatment of 2,3,4.6-tetra-O-acettyl-1-S-(Z)benzhydroximoyl-1-thio-D-glucopyranose with NBS under irradiation in carbon tetrachloride under refluxing conditions produced a spiro anomeric oxathiazole derivative in good yield. The synthesis of spiro[4,5]trienones was achieved via the intramolecular ipso bromocyclization of N-benzyl-N,3-diphenylpropiolamide.1778 In the presence of NBS, a variety of N-

the sequence of reactions, to reveal the stereochemistry of one regioisomer, tert-butyl 2-[(diphenylmethylene)amino]-3-phenylpent-4-enoate, some chemical transformations were carried out. For this, the sequential subjection of tert-butyl 2[(diphenylmethylene)amino]-3-phenylpent-4-enoate to hydrolysis and benzoylation produced the amido ester, which was converted to the 5,6-dihydro-4H-[1,3]oxazines by the reaction with NBS in dichloromethane at 0 °C (Scheme 627). The nuclear Overhauser effect (NOE) experiment of the products revealed that both products possess the 4S,5R-configuration. In the synthesis of 2,3,5-trisbustituted furans from α-formyl ketene dithioacetals, NBS-mediated cyclization to 2,3,5trisbustituted furans was described by Sasikala et al.1782 The reaction was carried out in a mixture of acetonitrile and water at room temperature for 24 h to achieve the corresponding furans in high yield (Scheme 628). Oxidative cyclization of 3-indolepropanethiol and 3-indolepropanol with NBS gave thiopyranoindole and pyranoindole, respectively, in high yield.1783 2,5-Difunctionalized 3,3dimethylpiperidines were prepared by Stevens et al.1784 They carried out addition reactions of nucleophiles to piperidinium salts, which were formed by electrophile-induced cyclization of γ,δ-unsaturated imines with NBS in an alcoholic medium (Scheme 629). Liu discovered a series of NBS-promoted 1,4-bromocyclization reactions for conjugated 1,3-enynes in the presence of a catalytic amount of DABCO (Scheme 630).1785 Various nitrogen nucleophiles could be added to conjugated enynes to generate bromoallenyl-substituted nitrogen heterocycles.

Scheme 622

Scheme 624 benzyl-N,3-diphenylpropiolamides underwent the intramolecular ipso halocyclization with water at 120 °C in acetonitrile, affording the corresponding bromo-substituted spiro[4,5] trienones in moderate to good yields (Scheme 625). A gold-catalyzed cyclization of β-amino ynone intermediates and halodeauration process enables an efficient one-step synthesis of halopyridone with NBS.1779 The relative reactivity of various functional groups toward alkyne electrophilic cyclization reactions was studied by Larocket al. (Scheme 626).1780 The required diarylalkynes have been prepared by consecutive Sonogashira reactions of appropriately substituted aryl halides, and competitive cyclizations have been performed using NBS electrophile. The reactions have been carried out

These processes led to simultaneous formation of a highly functionalized axially chiral allene and a stereogenic center. γ,δ-Unsaturated ketones undergo a very fast process of bromocyclization by treatment with NBS in methylene chloride solution at room temperature to produce the dibromodihydropyrans.1786 The reaction runs in a completely regioselective manner to furnish the dibromodihydropyrans in high yield (Scheme 631). 6951


Chemical Reviews

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An interesting bromoheterocyclization initiated by NBS results in the formation of bicyclic aziridine.1787 Sasaki and Yudin found that when 2-alkyl-3-(3-alkenyl)aziridine was treated with NBS in a mixed medium of 1,2- dimethoxyethane

Scheme 628

Scheme 625 catalyst, affording chiral oxazolines with a tetrasubstituted carbon center in high yield with up to 99% ee.1796 Wei et al. developed C−O bond formation via carboxylic acid-catalyzed reaction of 1-acetylcyclopropanecarboxamides with NBS, which provided 5-amino-3(2H)-furanones.1798 They carried out the reactions with 1-acetylcyclopropanecarboxamides at 80 °C in the presence of a catalytic amount of carboxylic acid (Scheme 634). (DME) and water, the reaction resulted in the formation of the corresponding 2-(1-bromoalkyl)-6-alkyl-1-azabicyclo[3.1.0]hexanes in good yields (Scheme 632).1787 They further extended this procedure for the synthesis of highly strained exobicyclic enamines via a base-mediated elimination of HBr.1788 This

Scheme 629

Scheme 626 Morra and Pagenkopf developed a method for the synthesis of 2,5-dibromo-1,1-dimethyl-3,4-diphenyl-1H-silole.1799 The procedure involves the initial treatment of dimethylbis(phenyScheme 630

method provided straightforward synthetic entries into a wide range of pyrrolidine- and piperidine-containing heterocycles. Following a similar process, Agami et al. synthesized a series of polysubstituted pyrroles from primary amines.1789 The key step of this process is the bromocyclization of δ-dienamino ester. The bromocyclization strategy can also be applied for the generation of substituted pyridines.1790 Bagley and co-workers synthesized 2,6-disubstituted 5-bromopyridine-3-carboxylates by Michael addition of enamino esters to ethynyl ketones followed by bromocyclization using NBS.1790 NBS is also suitably utilized for the synthesis of oxazoles.1791−1797 Treatment of alkenes with NBS, a nitrile, NaHCO3, and water in the presence of Cu(OTf)2 or Zn(OTf)2 was reported to furnish oxazolines in a one-pot reaction.1791 The reaction was carried out at room temperature and was found to be equally applicable to chalcones (Scheme 633).

lethynyl)silane with lithium naphthalenide in THF. The reaction mixture was further treated with anhydrous ZnCl2 followed by the addition of NBS to afford the desired product in high yield (Scheme 635). Peng et al. have shown a facile silver tetrafluoroboratecatalyzed electrophilic cascade cyclization reaction to generate bromo-substituted benzo[a]fluorenols using NBS under mild conditions (Scheme 636).1800 The process is highly chemoselective and proceeds in the presence of 5 mol % AgBF4 in DCM at 10 °C. Scheme 631

Scheme 627

Hewlett and Tepe reported the total synthesis of dibromophakellin via a one-pot addition of protected guanidine across a double bond mediated by NBS.1801 The reaction was carried out by treatment with 2.5 equiv of NBS in the presence of protected guanidine in a mixture of DCM and DMF at room temperature (Scheme 637). Pannecoucke and co-workers developed a method for the cyclization of β-selanyl amines using Meerwein salt or NBS to form various azetidine derivatives.1802−1804 Following a modification, they developed a synthetic approach for aziridine esters based on the cyclization of amino selanyl esters induced by the selanyl group activation with either the Meerwein salt or NBS.1805 The reaction was carried out by treating the precursor

Sun et al. developed a transition-metal-free method which involves ring opening of benzoxazoles with secondary amines and successive NBS-mediated oxidative cyclization, providing the formation of 2-aminobenzoxazoles.1793 NBS was used as a powerfull oxidant for this cyclization process. Yoshitaka et al. have carried out enantioselective bromocyclization of allylic amides with NBS in the presence of the DTBM−BINAP 6952


Chemical Reviews

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iminyl radical intermediate subsequently underwent a cyclization process. Yeung et al. reported NBS-induced multicomponent reactions involving ring-opening and ring-expansion cascades.1812−1815 They developed a general procedure for the electrophilic multicomponent cyclic ether ring-opening cascade using epichlorohydrin, an olefin, nosyl amide, and

Scheme 632

amino selanyl ester with 1.1 equiv of NBS in acetonitrile at room temperature followed by the addition of sodium bicarbonate. Chiral aziridine esters were also synthesized using this procedure. Mane and co-workers developed a onepot procedure for the synthesis of 2-aminothiazoles from aromatic acetophenones using NBS in PEG-400 at room temperature.1806 PEG-400 is also a good solvent for the ring bromination of salicylaldehyde.1807 The reaction was carried by the initial treatment of the aromatic acetophenones with a slight excess of NBS followed by the addition of an equimolar amount of thiourea. The reaction proceeds via the formation α-bromo ketones, which react further with thiourea to produce the final

Scheme 636

NBS.1812 The reaction was carried out by treating NsNH2 with olefin and NBS in epichlorohydrin at −30 °C for 16 h. This aminoalkoxylation process was found to be highly regioselective, and predominant formation of anti-Markovnikov product A over the Markovnikov product B was observed (Scheme 640). Finally, the halogenated product A was converted to

Scheme 633

Scheme 637 product. NBS-mediated radical cyclization processes have been reported.1808−1811 NBS, in combination with a catalytic amount of the radical initiator azoisobutyronitrile (AIBN), efficiently catalyzes a pseudo-four-component reaction (Scheme 638).1808 The process leads to the regioselective synthesis of σ-symmetric spiroheterobicyclic rings using aldehydes and urea in the presence of cyclic β-diesters or β-diamides such as Meldrum’s acid or barbituric acid derivatives. The reaction was carried out under solvent-free conditions at 80 °C. With AIBN, NBS was also found to be an efficient and regioselective reagent for the synthesis of 8-substituted xanthine derivatives at room temperature.1809 NBS (0.7 equiv) efficiently promoted the condensation of several aryl/cycloaryl/heteroaryl aldehydes with 5,6-diamino-1,3-dimethyluracils in the presence of a catalytic amount of AIBN (0.02 equiv) in a single step via a

2,2,6-trisubstituted morpholines by treatment with K2CO3 in acetonitrile at room temperature. The same group also carried out an NBS-mediated multicomponent aminocyclization process via aziridine ring expansion, which provided a highly stereoselective route toward the synthesis of azepane1813 and pyrollidines.1814 β,γ-Unsaturated hydrazones and vinylhydrazones are very suitable substrates to prepare pyrazoles in the presence of NBS.1816,1817 Xiao et al. recently carried out halocyclization of β,γ-unsaturated hydrazones with NBS.1816 Highly substituted 4,5-dihydropyrazoles were synthesiszed in good yield using CH2Cl2 as the solvent at room temperature. The method can be further employed for the synthesis of pharmaceutically important pyrazoles in a one-pot fashion. Wang1818 prepared 4bromo-2,5-dihydroisoxazoles from propargylic alcohols and Ntosylhydroxylamine using NBS in the presence of a catalytic amount of ytterbium triflate (Scheme 641). The reaction was carried out by treating propargylic alcohols with N-tosylhydroxylamine and NBS in the presence of 10 mol % Yb(OTf)3 in DCM at 25 °C. It was postulated that N-sulfonylallenamide forms as the key intermediate during the tandem transformation. Schomaker developed a method for the synthesis of nitrogen-containing stereotriads via a tandem aziridination/ ring-opening reaction of allenic sulfamates. 1819 Allenic sulfamates, on treatment with PhIO in the presence of a catalytic amount of Rh2(TPA)4 (TPA = triphenylacetate) in DCM at room temperature, produced a strained (E)-bicyclic

Scheme 634

radical chain reaction (Scheme 639). A mixture of CH3CN and water (9:1) is a suitable solvent system for the process. The research group of Zhang has applied the NBS-assisted radical cyclization process for different azides such as 2-azidoN-phenylacetamides1810 and 3-arylallyl azides1811 under visible light irradiation. In both cases, the bromine radical from NBS leads to the formation of an iminyl radical via α-hydrogen abstraction and subsequent extrusion of dinitrogen. The key Scheme 635

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reaction was carried out in the presence of sodium nitrite and acetic anhydride within 4−5 h in dichloromethane at 0−5 °C. Cook and Chung found that 3-bromo-5,5-dimethylhydantoin can be used for the bromolactonization of γ,δ-unsaturated acids.1827 The reaction was performed by treating the olefin with 3-bromo-5,5-dimethylhydantoin in DME at room temper-

Scheme 638

Scheme 641

methylene aziridine which undergoes a nucleophilic ringopening reaction to form (E)-enesulfamates. These enesulfamates are sufficiently nucleophilic to react with NBS in the presence of a reductant, NaBH3CN, to form the stereotriad in high yield (Scheme 642). The whole process can be carried out in situ. It can also be carried out by initially synthesizing the enesulfamates. The process is highly diastereoselective.

ature. Cook and Kang reported a similar method for bromolactonization using N-bromophthalimide.1828 Rievera reported a suitable method for the synthesis of 5-substituted 2-amino-1,3,4-oxadiazoles, as biologically active important molecules, via oxidative cyclization of thiosemicarbazides using DBH.1829 The oxadiazoles were produced by treating the thiosemicarbazides with DBH in the presence of potassium iodide and sodium hydroxide in 2-propanol as the reaction medium at low temperature (Scheme 645). The main advantage of this method is its applicability for the large-scale synthesis of the oxadiazoles. Wu et al. used tetrabutylammonium tribromide (TBATB) to synthesize 6-bromocoumarins.1830 A range of 6-bromocoumarins were synthesized via a one-pot, three-component reaction of phenols, 4-substituted acetoacetate, and TBATB in a 1:1:1 ratio in a mixed medium of dichloromethane and methanol (Scheme 646). The reaction takes about 6−8 h for completion at room temperature to furnish the coumarins in high yield. The salicylaldehydes underwent cyclization with bromonitromethane to give the benzofurans, where cis- and transhydroxybenzofuran were formed as intermediates.1831 Jordan and co-workers described a method for the synthesis of 2aminobenzothiazoles using an equimolar amount of benzyltrimethylammonium tribromide from aryl thioureas in acetic acid. For example, 4-methylphenylthiourea was reacted with benzyltrimethylammonium tribromide in acetic acid for 18 h to provide aminobenzothiazole in 69% yield, and 2-methylamino6-bromobenzothiazole was also prepared in 75% yield (Scheme 647).1832 Han and co-workers used this reagent for the synthesis of bromoalkyl-branched imidazolines by using CuI−PPh3 as the catalyst and N,N-dibromo-p-toluenesulfonamide as the nitrogen as well as halogen source (Scheme 648).1833 This reaction has a good substrate scope which can convert alkenes such as α,β-unsaturated ketones, α,β-unsaturated esters, and simple olefins to the corresponding imidazolines. Sayama et al. have carried out the synthesis of various 2oxazolines from aromatic aldehydes and 2-aminoethanol with pyridinium hydrobromide perbromide in water at room temperature. Under the same reaction conditions, aromatic aldehydes with ethylenediamine provide 2-imidazolines in good yields.1834 Shen et al. again carried out another electrophilic addition reaction of (Z)-alk-2-en-4-ynoates with TsNBr2 as the brominating agent (Scheme 649).1835 The procedure reported a facile and highly stereoselective synthesis of densely functionalized aziridine derivatives. This was an unprecedented highly regio- and stereoselective electrophilic addition reaction of (Z)-alk-2-en-4-ynoates with TsNBr2.

Scheme 639

Ma et al. have successfully carried out the electrophilic cyclization of allenes with NBS.1820−1822 Tertiary 2,3allenoals 1820 provided 3-bromo-2,5-dihydrofurans with MeCN−H2O (15:1) as the solvent, while diaryl 2,3-allenyl ethers1822 provided highly functionalized 2-bromonapthalene products in the presence of CH3NO2−EtOH (3:1). Gulder had shown an iodine(III)-catalyzed bromocarbocyclization process to produce 3,3-disubstituted oxoindoles. N-Aryl-N-methylacrylamides were subjected to bromocarbocyclization in the presence of o-iodobenzamide (10 mol %) as the catalyst in the presence of NBS (1.2 equiv) and NH4Cl (10 mol %) in DCM at room temperature to produce oxoindoles in high yield (Scheme 643).1823 Cyclohexanones and ethanedithiol or 2-mercaptoethanol undergo a cyclization reaction in the presence of NBS at 0 °C to produce 1,4-dithiane or 1,4-oxathiane compounds.1824 α,β-Unsaturated aromatic carboxylic acids, upon treatment with NBS and a catalytic amount of group I metal acetates, give βScheme 640

bromostyrenes, while the corresponding reactions of α,βunsaturated aromatic amides lead to α-bromo-β-lactams.1825 The use of 20 mol % NaOAc in aceotonitrile−water was found to be suitable for the synthesis of the lactams. However, the yield of the reaction was not very impressive. 6.3. Cyclization Reactions Using Other Bromo Compounds

Bisbromine−1,4-diazabicyclo[2.2.2]octane (Br2−DABCO) was found to promote the one-pot conversion of various Narylglycines to sydnones in combination with NaNO2 and Ac2O. The synthesis proceeds efficiently through N-nitrosation followed by cyclization in high yields (Scheme 644).1826 The 6954


Chemical Reviews

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Scheme 642

1,3-Dibromo-5,5-dimethylhydantoin (DBDMH) is a good source for the cyclization process.1836−1838 Fujioka developed a

potassium carbonate (Scheme 651). β,β-Bromonitrotrimethylenicglycol could be obtained by the action of formaldehyde on bromonitromethane; however, the process results in the formation of bromonitroethylic alcohol in the presence of potassium carbonate. Similarly, β,β-bromonitroisopropylic alcohol was obtained from bromonitromethane and acetaldehyde. It was found that, β,β-bromonitrobutylenic α−γ-glycol could be prepared either by reaction of acetaldehyde and

Scheme 644

Scheme 647

Scheme 643

bromonitroethylic alcohol or by the action of formaldehyde on bromonitropropylic alcohol. Bromonitromethane adds to aliphatic aldehydes in the presence of tin(II) chloride to yield β-nitro alcohols via a

method for performing enantioselective bromolactonization reactions of trisubstituted alkenoic acids using the C3symmetric trisimidazoline and DBDMH as a bromine source (Scheme 650).1836 The process leads to the formation of chiral δ-lactones containing a quaternary carbon. (Z)-Olefins were found to be favorable substrates for the process. Cyclic trisubstituted olefins result in the formation of chiral spirocyclic lactones. A high level of enantioselectivity was observed during the process. In comparison to N-bromophthalimide-, Nbromoacetamide-, and N,N-dibromoisocyanuric acid-mediated bromolactonization, the process with DBDMH was found to be more effective in terms of enantioselectivity.

Scheme 648

Reformatsky-type reaction in high yields, while aromatic aldehydes produce low yields.1840 Nitrocyclopropane formation has been successfully carried out by the reaction of bromonitromethane with electrophilic alkenes bearing two electron-withdrawing groups in the α- and β-positions in the presence of potassium carbonate as a base (Scheme 652).1841 The method allows good yields and moderate to satisfactory diastereoselectivity with linear alkenes, while it shows the complete formation of the exo product with N-alkylmaleimides. A general organocatalytic enantioselective synthesis of nitrocyclopropanes from bromonitromethane and a variety of

Scheme 645

Scheme 649

7. FORMATION OF NITRO COMPOUNDS 7.1. Formation of Nitro Compounds Using Bromonitromethane

Maas developed a procedure for the preparation of nitro alcohols using bromonitromethane..1839 In this process, β,βbromonitroethylic alcohol was prepared by the condensation of bromonitromethane with formaldehyde under the influence of

cyclic and acyclic enones was described by Ley (Scheme 653).1842 The reaction was carried out by treating bromonitromethane with chalcones in the presence of 5-((R)-pyrrolidin-2yl)-1H-tetrazole and morpholine to furnish the corresponding enantioenriched nitrocyclopropanes in high yield. A one-pot procedure was developed by Kirsch and coworkers to prepare new 2-aryl-5-nitrothiophenes efficiently from bromonitromethane and 3-chloro-3-arylpropenals (Scheme 654).1843 Nitrothiophenes were synthesized in good yields by reacting 3-chloro-3-arylpropenals with bromonitro-

Scheme 646

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Scheme 650

Scheme 653

for the synthesis of 2-nitroamines via an indium-promoted reaction of bromonitromethane with imines.1850

methane in the presence of sodium sulfide and aqueous sodium hydroxide. An easy preparation of substituted 3-amino-2-nitrothiophenes and -selenophenes was described (Scheme 655).1844 Substituted β-chloroacrylonitriles were reacted with sodium sulfide or sodium selenide and bromonitromethane to yield the expected compound in a one-pot three-step procedure in good yields. A facile one-step synthesis of 2-nitro-3-aminobenzofuran by the reaction of salicylonitrile with bromonitromethane in acetone in the presence of anhydrous potassium carbonate was reported by Harwalkar et al.1845 A process for the preparation of [1α,5α,6α]-6-nitro-3-benzyl-2,4-dioxoazabicyclo[3.1.0]hexane was reported by Madhusudhan.1846 The reaction was carried out by treating N-benzylmaleimide with bromonitromethane in the presence of an amidine base such as

Direct nitration of phenol with NaNO2 was achieved in the presence of DBH and wet SiO2.1852 All reactions were

Scheme 651

Scheme 655

7.2. Use of Other Bromo-Organic Compounds for the Formation of Nitro Compounds

Niknam et al. reported that nitrophenols could be obtained via direct nitration of phenols with tribromoisocyanuric acid, NaNO2, and wet SiO2 at room temperature in good to high yields (Scheme 658).1851 Scheme 654

N,N-diethylacetamidine to furnish the product in good yield. A method to obtain racemic 1-nitroalkan-2-ols by the reaction of bromonitromethane with a variety of aldehydes promoted by SmI2 was reported by Concellón et al.1847 The reaction was carried out by the treatment of bromonitromethane with a carbonyl compound in the presence of SmI2 in THF as the reaction medium at room temperature. The chiral version of the reaction has also been performed with chiral N,Ndibenzylamino aldehydes, affording the corresponding enantiopure 3-amino-1-nitroalkan-2-ols with good stereoselectivity (Scheme 656). In the presence of tin(II) chloride, bromonitromethane reacted with imines derived from aromatic aldehydes and ammonia to yield 2-amino-2-aromatic-substituted nitroethane derivatives via an addition reaction in good yields.1848 ́ Rodriguez-Solla et al. found that bromonitromethane undergoes the aza-Henry reaction with a variety of imines in the

performed by treating equimolar amounts of both NaNO2 and DBH in the presence of 40 wt % wet SiO2 at room temperature under completely heterogeneous conditions (Scheme 659). In the same manner, when N,N-dialkylamines were treated with the DBH/NaNO2/wet SiO2 reagent system, their corresponding N-nitrosated derivatives were obtained in good to excellent yields.1853 The reactions were carried out with a suspension of sodium nitrite, DBH, and amine in the presence of wet SiO2 in dichloromethane at room temperature. For example, 4-nitrosomorpholine was synthesized by treating morpholine with 0.6 mol equiv of DBH and 2 mol equiv of NaNO2 in the presence of 50 wt % of wet SiO2 at room temperature (Scheme 660). A successful nitration process has also been achieved in the presence of NBS.1854−1856 Froyen developed a method for the conversion of alcohols to the corresponding nitrates using silver nitrate in the presence of NBS.1854 He found that the treatment of alcohols with triphenylphosphine, NBS, and silver nitrate affords the corresponding alkyl nitrates in excellent yields. Ridd et al. developed an effective protocol for the nitration of phenols using 4-methyl-4-nitro-2,3,5,6-tetrabromocyclohexa2,5-dienone in diethyl ether (Scheme 661).1857 The reaction proceeds via a radical process involving reaction between the phenoxyl radical and NO2 radical.

Scheme 652

presence of SmI2 and NaI to afford nitroamines or bromonitroamines, respectively (Scheme 657).1849 The reaction was carried out by mixing the bromonitromethane (1 equiv), SmI2 (1 equiv), and imine (1 equiv) in THF at room temperature. However, when the reaction was carried out using a catalytic amount (15 mol %) of NaI, 2-amino-1-bromo-1nitroalkanes were obtained in high yield. Sugar-based imines undergo the reaction in high yields and exhibit moderate to good stereoselectivities. A similar protocol was also developed

Scheme 656

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Chemical Reviews

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treatment with NH3 furnished N-tosyl-1,2,3,9a-tetrahydrocarbazole. The reaction of N-mesyl-1,2,3,9a-tetrahydrocarbazole with CuBr2 in methanol afforded N-mesyl-4-methoxy-1,2,3,4-

A method for the nitration of aromatic compounds was developed by Nowrouzi1855 by using NBS and silver nitrate as a convenient reagent system. The reaction was carried out by refluxing a mixture of the aromatic compound, NBS, and

Scheme 660

Scheme 657

tetrahydrocarbazole. N-Mesyl-6-methyl-2-(1-cyclopenten-1-yl) aniline in a reaction with bromine in the presence of NaHCO3 was oxidized into the corresponding cyclopentenone, and with NBS, it gave N-mesyl-2-(2-bromo-1-cyclopenten-1-yl)aniline. N-(Bromocarbamoylmethyl)benzamides were prepared by treating a solution of N-(cyanomethyl)acetamide with bromine in acetic acid. For example, 4-chloro-N-(cyanomethyl)benzamide was treated with bromine in acid to give the corresponding brominated product in 89% yield (Scheme 664).1862

AgNO3 in equimolar amounts in acetonitrile for about 3−7 h (Scheme 662).

8. REARRANGEMENT REACTIONS 8.1. Molecular Bromine-Assisted Rearrangement Reactions

Nagakura reported that the allyl alcohol bearing a methyl and a tert-butyl group at the hydroxylated position undergoes a rearrangement when treated with bromine in an aqueous medium to afford a product mixture containing two regioisomeric ketones and one oxirane. For example, the reaction of 3,4,4-trimethyl-2-alkylpent-1-en-3-ol with bromine in an aqueous medium resulted in rearrangement, yielding ketones 4-(bromomethyl)-2,2-dimethylpentan-3-one and 3(bromomethyl)-4,4-dimethyl-3-alkylpentan-2-one and the oxirane.1858 Baklan reported that the Beckmann rearrangement of

Scheme 661

Scheme 658

Primary amides when treated with bromine in the presence of a base such as sodium hydroxide produce amines as the products. This reaction is known as Hofmann rearrangement or Hofmann degradation (Scheme 665).1863 The reaction proceeds through the intermediate isocyanate, which is seldom Scheme 662

1-adamantyl methyl ketone oximes occurs in liquid bromine.1859 The cesium flouride-assisted reactions of syn- and anti-N-fluoro-1-cyano-1-fluoromethanimine with bromine was described by Mir et al.1860 Under this reaction condition, the more reactive syn isomer is isomerized to the anti isomer, and consequently, the reaction results in bromofluorination.

isolated since it is usually hydrolyzed under the reaction conditions to give the corresponding amine. In the preparation of 3-aminopyrrolidine, Hirose et al. carried out a reaction with 1-(ethoxycarbonyl)-3-pyrrolidinecarboxamide with bromine in aqueous potassium hydroxide followed by hydrolysis to produce 3-amino-1-(ethoxycarbonyl)pyrrolidine (Scheme 666).1864 He et al. developed a multistep process for the synthesis of [2-(2-thienyl)ethyl]amine. In the final step of the reaction sequence, 3-(2-thienyl)propionamide was reacted with bromine in aqueous NaOH at 0 °C for 0.5 h and then hydrolyzed to obtain the desired product.1865

Scheme 659

Gataullin et al.1861 reported the reaction of N-mesyl-2-(1methyl-1-butenyl)-6-methylaniline with bromine to afford Nmesyl-2-(3-bromo-1-penten-2-yl)aniline, which, on further treatment with NH3 or amines, undergoes cyclization to Nmesyl-7-methyl-3-methylene-2-ethylindoline (Scheme 663). Similarly, N-tosyl-2-(1-cyclohexen-1-yl)aniline was converted into N-tosyl-2-(6-bromo-1-cyclohexen-1-yl)aniline, which on

8.2. Rearrangement Reactions Using NBS

Hofmann rearrangement of amides can also be achieved using NBS. Treatment of primary amides with NBS in a mixture of an alcohol and DMF in the presence of sodium acetate produces the corresponding urethanes.1866 For example, treatment of 6957


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pentenyl oxime derivatives proceeds in good yield under mild conditions through the formation of a cationic tetrahydrofuranium intermediate in the halocyclization reaction with NBS.1874 For example, the rearrangement of acetophenone O-(4pentenyl) oxime produces N-phenylacetamide in excellent yield (Scheme 671). A new type of rearrangement process of spirocyclic cyclobutane N-halo aminals was described by Murai et al. (Scheme 672).1875 Bicyclic amidines were produced in this

pivalamide with NBS, NaOAc, and benzyl alcohol produces benzyl tert-butylcarbamate in 57% yield (Scheme 667). Later, Jew et al. found that the addition of Hg(OAc)2 to the reaction of the carboxamide with alcohol and NBS in DMF has a beneficial effect in improving the yield.1867 They also reported the use of HgO instead of Hg(OAc)2 for this reaction.1868 Senanayake et al. unvailed the nature of NBS in basic media.1869 Scheme 663

Scheme 667

They reported that NBS in basic media is the true oxidizing species in the Hofmann rearrangement. With a base, NBS generates a species which acts as an oxidizing agent. The reactions were carried out with an aminonicotinamide using NBS in the presence of KOH in methanol at −5 °C to produce a 60% yield of the rearranged product (Scheme 668). The treatment of a series of α,α-disubstituted α-hydroxy amides with NBS in the presence of silver acetate in DMF or MeCN at room temperature afforded the corresponding ketones in high yields.1870 For example, benzophenone was obtained in 100% yield from the rearrangement of 2-hydroxy2,2-diphenylacetamide (Scheme 669). The use of sodium methoxide and DBU base in methanol at reflux temperature has also been reported for the NBSpromoted Hofmann rearrangement (Scheme 670).1871−1873

process by a pathway involving initial N-halogenation of one of the aminal nitrogens followed by cyclobutane ring expansion through 1,2-C-to-N migration with simultaneous N−X bond cleavage. This reaction was achieved by the treatment of the aminals with NBS in dichloromethane. Another spiro rearrangement reaction was carried out by Yancaho et al. to prepare indolyldiketopiperazines.1876 The rearrangemet reaction was carried out under acidic condition. Kelly et al. carried out an oxidative rearrangement that enables the selective preparation of diverse 2-substituted 3-furfurals (Scheme 673).1877 The 3-furfural generates a furyl alcohol on Scheme 668

Scheme 664

the addition of an organometallic reagent. Oxidative rearrangement of the furyl alcohol with NBS provides the desired 2substituted 3-furfurals without contamination by other isomers. Ma et al. carried out the rearrangement of 2,3-allenols with NBS to obtain a 1,2-shift product.1820,1821 They observed that the electrophilic reaction of terminal tertiary 2,3-allenols with

Huang and Keillor reported that the reaction of parasubstituted aromatic and primary aliphatic carboxamides with NBS and NaOMe in methanol at reflux temperature for 10 min results in the conversion of the carboxamides to their Scheme 665

Scheme 669

corresponding primary amino methyl carbamates in nearly quantitative yields.1871 This modified Hofmann rearrangement was shown to be particularly useful for the preparation of parasubstituted anilines. They improved the procedure by using DBU instead of NaOMe for the production of methyl carbamate via the Hofmann rearrangement.1872,1873 Amides such as 4-methoxybenzamide, 3,4-dimethoxybenzamide, 4-methylbenzamide, and 4-chlorobenzamide underwent Hofmann rearrangement on treatment with NBS and DBU in methanol to give the carbamate in good yields. Beckmann rearrangement of O-4-

NBS in water afforded 2-bromoallylic ketones highly selectively in up to 97% yields.1820 When both R1 and R2 (the substituents on the carbon atom connected to the hydroxyl groups) are alkyl groups, one of these two groups migrates. With 1,2propadienylcycloalkanols, a ring expansion reaction was observed. with R1 being an aryl group, R1 would be transferred exclusively to form the 2-bromoallylic ketones. Again, these 2bromo-1-aryl-2-propenyl ketones can be converted into 1,2-

Scheme 666

Scheme 670

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2-(bromomethyl)-4-methylpent-2-enoate in good yield (Scheme 679).1885 In an attempt at a formal synthesis of laureatin, Howell1886 showed an unexpected skeletal rearrangement of oxetane alcohol mediated by NBS, leading to the formation of epoxytetrahydrofuran rather than the formation of the expected laureatin core (Scheme 680). Lindel carried out the rearrangement of 2-tert-prenyltryptamines. This method is very effective to synthesize flustramine C, which is a marine natural product.1887

allenyl ketones after column chromatography on silica gel preeluted with a few drops of Et3N. When there is at least an alkyl substituent on the 4-position of the tertiary 2,3-allenols, their electrophilic reaction with NBS in CH3CN/H2O in a ratio of 15:1 or H2O, under the same reaction conditions as above, affords 3-bromo-2,5-dihydrofurans (Scheme 674). In the total synthesis of (±)-lycoramine and some certain Amaryllidaceae alkaloids, Tu et al. carried out NBS-mediated semipinacol rearrangement.1878−1880 The allylic alcohols were subjected to semipinacol rearrangement by reaction with NBS in 2-propanol or isobutanol at room temperature to obtain the synthetic precursor (Scheme 675). Meijer et al. studied the reaction of NBS and tert-butyl hypochlorite with tetraalkylethylene.1881 They observed rearrangements during the bromination reaction. Bromo cation addition to the double bond occurred in a fast reaction,

8.3. Rearrangement Reactions in the Presence of Other Bromo-Organic Compounds

When 1,3-dithiolanes bearing a phenyl or substituted aromatic group and a methyl (or methylene) group attached to C-2 were treated with DBH in the presence of HF/pyridine, a rearrangement took place instead of gem difluorination.1888 The reaction was carried out by treating the substrate with DBH in dichloromethane at room temperature under a nitrogen atmosphere (Scheme 681). Regiospecific bromination−rearrangement of the 5-substituted 2-alkylidene-4-oxothiazolidine derivatives induced by pyridinium hydrobromide perbromide (PHBP) provides a new synthetic approach to the corresponding push−pull thiazolidines with two exocyclic double bonds (Scheme 682).1889 In comparison to a heterogeneous alternative, this conversion, taking place in acetonitrile under homogeneous reaction conditions, has the advantage of almost quantitative yields and a substantial rate enhancement. Tribromoisocyanuric acid can be used for the Hofmann rearrangement reaction.1890 Miranda developed a protocol for microwave-assisted Hofmann rearrangement mediated by tribromoisocyanuric acid/KOH/MeOH. Under this condition, they obtained a good yield of aromatic benzamides in a very short period of time (Scheme 683). We have developed a method for the synthesis of methyl carbamate via Hofmann rearrangement in the presence of TsNBr2.1891 Carbamates were synthesized from the corresponding amides in the presence of DBU in methanol using TsNBr2. The reaction was complete in 10−20 min at reflux temperature to produce the corresponding carbamates in excellent yield (Scheme 684). In general, this procedure works well for a variety of aromatic as well as aliphatic amides to produce the corresponding carbamate in excellent yield. Besides methanol, other primary alcohols were also successfully used for the reaction. However, secondary alcohols could not induce the transformation under the same reaction conditions. Shen et al. presented a reaction pathway of 2,3-allenoates with an electrophile, TsNBr2, in the presence of K2CO3 to produce (1E,2E)-3-bromo-4-oxo-N′tosyl-2-alkenoxylimidic acid ethyl esters. The reaction proceeds in a highly stereoselective fashion (Scheme 685).1892 During the bromination of securinine with 1,3-dibromo-5,5dimethylhydantoin in methanol, an interesting and surprising rearrangement was observed (Scheme 686). A stereoselective ring contraction product (norsecurinine derivative) was observed during the course of bromination.1893 The reaction occurs through the formation of a β-bromo enamine intermediate. Bromodimethylsulfonium bromide (BDMS) was found to be a very efficient reagent for Lossen rearrangement of hydroxamic acids to the corresponding isocyanates (Scheme 687).1894

Scheme 671

followed by abstraction of an allylic proton, resulting in a double bond shift. Treatment of (+)-methylene camphor with NBS in the presence of pyridine resulted in a rapid Scheme 672

rearrangement to yield a brominated (+)-methylenefenchone in high yield and purity (>96%) (Scheme 676).1882 A combination of NBS and dibenzoyl peroxide or azobis(isobutyronitrile) was used to carry out the isomerization of (Z)-alkenes to the corresponding (E)-alkenes.1883 The reaction was carried out by heating the allkene with 1.1 equiv of NBS in the presence of AIBN in CCl4 at reflux temperature for 1 h (Scheme 677). Hurley and Dake investigated a synthetic route incorporating an NBS-promoted semipinacol rearrangement to the 6azaspiro[4.5]decane fragment within halichlorine.1884 They Scheme 673

carried out the synthesis by treating a substituted 1-(1,4,5,6tetrahydro-1-tosylpyridin-2-yl)-2-alkylcyclobutanol with NBS in 2-propanol to produce the target molecule (Scheme 678). Bennett and Paquette studied the reaction of NBS with methyl 3-hydroxy-4-methyl-2-methylenepentanoate in the presence of dimethyl sulfide. The reaction was carried out by adding NBS to a mixture of methyl 3-hydroxy-4-methyl-2methylenepentanoate and dimethyl sulfide in dichloromethane at 0 °C, and the reaction was continued at room temperature for 24 h. The reaction afforded the corresponding methyl (Z)6959


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Scheme 674

Scheme 675

Scheme 676

Scheme 681

Scheme 677

Scheme 682

Scheme 678

bromine. They found that the use of copper acetate and bromine in methanol produced the best yield of the product.1895 Patrocinio et al. developed an oxidative method for the hydrolysis of 1,3-dithianes to produce acylsilanes.1896 The reaction was carried out by treating the 2-silyl-1,3-dithianes with 4−6 equiv of NBS in aqueous acetone or acetonitrile to provide acylsilanes with good yields (40−96%) in a short reaction period. In the enantioselective synthesis of β-hydroxy-

Scheme 679

Scheme 683 Isocyantes were trapped in situ with various amines to afford unsymmetrical ureas in good to excellent yields (64−89%).

9. HYDROLYSIS REACTIONS Hydrolysis of 2-(phenylhydrazono)-1-(phenylamino)butane1,3-dione was examined by Agarwal and Agarwal. They screened several combinations of catalysts in the presence of

γ-keto esters by ester enolate aldol reactions with 2-acyl-2-alkyl1,3-dithiane 1-oxides, Ruano et al.1897 used NBS for the hydrolysis of the 1,3-dithiane 1-oxide moieties of the

Scheme 680

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under this condition. Addition of a base is essential in this reaction as the reaction proceeds through Rh25+-catalyzed aminobromination and subsequent base-induced ring closure. Michida and Sayo developed a similar procedure for the synthesis of N-sulfenylaziridines using NBS as the oxidant.1900 The reaction proceeds via an in situ generated 2,4dinitrobenzenesulfenylnitrene, produced by the oxidation of 2,4-dinitrobenzenesulfenamide with NBS, which was trapped as an N-sulfenylaziridine, in the presence of a large excess of olefins. Chloramine-T (TsNClNa·3H2O) was found to be very effective for the aziridination of olefins in the presence of bromine-based catalysts, including NBS,1901,1902 PhNMe3Br3,1903,1904 Py·HBr3,1905 and HBr.1906 NBS can effectively catalyze the aziridination of electron-deficient as well as electron-rich olefins using chloramine-T as a nitrogen source under ambient conditions in good to excellent yields.1901 Thakur and Sudalai carried out this reaction by treating the olefin with chloramine-T trihydrate in the presence of 20 mol % NBS in acetonitrile at room temperature. They also used Nbromoacetamide as the catalyst for the aziridination reaction with chloramine-T. Jain and Sain later improved this NBScatalyzed aziridination reaction using an ionic liquid.1902 They carried out the reaction using ionic liquids as recyclable reaction media in the presence of a catalytic amount of NBS and chloramine-T as the nitrene donor. The reaction was found to

diastereoisomerically pure adducts ((+)-ethyl [2′R,2S,3R,(S) R]-3-(2′-ethyl-1′-oxo-1′,3′-dithian-2′-yl)-3-hydroxy-2-methylbutanoate, (+)-[2″R,1′S,3R,(S)R]-3-[1′-(2″-ethyl-1″-oxo-1″,3″dithian-2″-yl)-1′-(hydroxy)ethyl]tetrahydrofuran-2-one, Scheme 684

(+)-ethyl [2′R,2S,3R,(S)R]-3-(2′-ethyl-1′-oxo-1′,3′-dithian-2′yl)-5-phenyl-3-hydroxy-2-methylpentanoate, (+)-[2″R,1(S,3R, (S)R]-3-[1′-(2″-ethyl-1″-oxo-1″,3″-dithian-2″-yl)-3-phenyl-1hydroxypropyl]tetrahydrofuran-2-one) in a 9:1 acetone−water mixture to give the corresponding enantiomerically enriched βhydroxy-γ-keto esters (Scheme 688). Oxidative hydrolysis of various vinyl halides affords the corresponding α-halomethyl ketones in the presence of aqueous NBS with good yield and purity.1898 Scheme 685

Scheme 688

Scheme 686 be very fast to produce the corresponding aziridines from olefin in high yield. Sharpless, followed by Peter O’Brien, developed a method for the aziridination of olefins using phenyltrimethylammonium tribromide (PhNMe3+Br3−) as the catalyst using anhydrous TsNClNa.1903,1904 The actual catalyst for this reaction is bromine, which promotes the reaction in acetonitrile at room temperature. Sudalai and co-workers also developed another method for the aziridination of electron-deficient as

10. AZIRIDINATION REACTIONS Doyle et al. described a mild, efficient, and selective aziridination of olefins catalyzed by dirhodium(II) caprolactamate (Scheme 689).1899 The synthesis was achieved by treating the olefin with TsNH2, NBS, and potassium carbonate in the presence of 0.01 mol % catalyst in DCM at room temperature for 12 h. Although olefins such as styrenes and terminal and cyclic olefins could be converted to the respective aziridines in moderate to high yields, cinnamates are found to be inactive

Scheme 689

well as electron-rich olefins using chloramine-T as a nitrogen source in the presence of pyridinium hydrobromide perbromide as the catalyst.1905 The reaction proceeds smoothly at room temperature to afford the corresponding aziridines in moderate to good yields. NBS was found to be an efficient catalyst for condensations of indoles with aldehydes or ketones under sovent-free conditions.1907 Chanda et al. reported that, in the presence of a copper catalyst, different aziridines could be prepared from olefins using bromoamine-T (TsNBrNa) as a source of nitrene. They carried out a detailed investigation of

Scheme 687

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acrylate, cyclohexenone, ethyl cinnamate, etc., which produced the corresponding aziridine in high yields.

the aziridination reaction with bromamine-T in the presence of a variety of transition-metal catalysts under microwave and ultrasound irradiation.1908 Both CuCl2 and CuBr2 were found to be efficient catalysts under this condition. However, the copper-catalyzed aziridination of methyl cinnamate with bromamine-T did not proceed at ambient temperature. The use of ultrasound irradiation could furnish trans-aziridine selectively in low yield, while, under microwave irradiation, a mixture of cis and trans isomers was obtained. They also prepared aziridines from olefins with bromamine-T in the presence of a bleaching powder (i.e., calcium hypochlorite) under an inert atmosphere.1909 Later, they modified the bromamine-T-mediated aziridination process using heterogeneous catalysts such as zeolite Hβ1910 and a polymer-supported Mn(II) complex.1911 The same reagent has also been used for the aziridination of olefins in the presence of palladium (Scheme 690).1912 The palladium(II)-promoted reaction of a variety of olefins and bromamine-T in acetonitrile at room temperature provided 2-substituted N-tosylaziridines under mild conditions. Olefins such as cinnamates, N,N-dimethylacrylamides, acrylonitrile, chalcone, etc could be transformed into the corresponding aziridines at room temperature in low yield. Olefins bearing chiral appendages gave only a poor to modest diastereoselectivity.1913 Jain and Sain used bromoamine-T as a nitrene precursor using copper, manganese, and iron phthalocyanines as catalysts for the aziridination of olefins.1914 In the presence of Fe(II)− and Mn−porphyrin complexes as catalysts, the aziridination of alkenes using bromamine T proceeds with moderate to low stereospecificity.1915,1916 Cobalt porphyrins are also capable of catalyzing the aziridination of alkenes with bromamine-T as the nitrene source.1917 The catalyst could activate a variety of olefins in acetonitrile at room temperature with excellent yield to produce the N-sulfonylated aziridine along with NaBr as the byproduct. Our group developed a fast and efficient method for the aziridination process using iodine as the catalyst with bromamine-T. The method is easy to perform at room temperature and is applicable to various olefins to give the corresponding aziridines in high yield. The use of 10 mol % iodine is sufficient to promote the transformation in the forward direction for completion.1918 A catalyst-free aziridination process has also been reported.1919,1920 We have used N,Ndibromo-p-toluenesulfonamide for the aziridination of various types of olefins in the presence of a base without any catalyst.1919 The reaction was performed by treating the olefin with 1.2 equiv of olefin in the presence of 2.5 equiv of potassium carbonate (Scheme 691). The reaction proceeds well at room temperature to afford the corresponding Nsulfonylated aziridine in a short time. However, cinnamates reacted slowly as compared to styrenes. The reaction proceeds via the formation of a nitrene from N,N-dibromo-ptoluenesulfonamide by debromination in the presence of a base. We extended the procedure to various kinds of olefins such as indene, β-methylstyrene, cyclohexene, 1-octene, ethyl

11. RING-OPENING REACTIONS A procedure for the preparation of halo diols by the opening of epoxy alcohols with halogen in the presence of Ti(OCHMe2)4 is described by Alvarez et al. By this method, regioselective cleavage of allylic and homoallylic epoxy alcohols was achieved with bromine to produce the corresponding bromohydrins in high yield (Scheme 692).1921 The bromohydrins and aryl bromides were prepared by brominating an equimolar mixture of the oxirane and bromine at 250−350 K followed by separation of the resulting bromohydrins and aryl bromides.1922 The regioselective ringopening halogenation of some epoxides using elemental bromine in the presence of a series of new synthetic macrocyclic diamides and also in the presence of dibenzo-18crown-6, 18-crown-6, and aza-18-crown-6 was studied by Sharghi et al.1923 The epoxides were subjected to cleavage by liquid bromine in the presence of these catalysts in dichloromethane at room temperature. The individual bromohydrins were synthesized in high yield and with more than 95% regioselectivity. Methyl- and phenyl-substituted (ethoxycarbonyl)azabicyclo[2.2.0]hexenes reacted with the bromohydrins, the reaction involving the ring cleavage of exo-epoxide derivatives with bromine in the presence of Ph3P.1924 For example, the parent 5,6-exo-epoxide and 5-endo-methyl 5,6-exo-epoxide were ring opened with bromine/triphenylphosphine to afford 5-endobromo-6-exo-hydroxy-2-azabicyclo[2.2.0]hexanes, while the 3Scheme 691

endo-methyl epoxide afforded solely the rearranged 5-antibromo-6-anti-hydroxy-3-exo-methyl-2-azabicyclo[2.1.1]hexane isomer (Scheme 693). The action of bromine on 2-amino-4-[4-(butanoyloxy) phenyl]-7,7-dimethyl-3-cyano-5,6,7,8-tetrahydrobenzo[b] pyran-5(4H)-one in a mixture of methanol and water as the reaction medium resulted in the ring opening to the methyl 2cyano-3-(4-hydroxyphenyl)-3-(4,4-dimethyl-2,6-dioxocyclohex1-yl)acrylate.1925 The regioselective ring-opening halogenation of some epoxides using elemental bromine in the presence of a series of pyridine-containing groups was studied by Sharghi et al.1926 The epoxides were subjected to cleavage by elemental bromine in the presence of isonicotinic hydrazide (isoniazide) in THF at room temperature. The individual halohydrins could be synthesized in high yield and with more than 95% regioselectivity (Scheme 694). Trisubstituted terpene and aryl-substituted epoxides react with bromine and dimethyl sulfide to afford α-bromo ketones or α-bromo aldehydes as the major products in good yields (Scheme 695). The reaction is regiospecific and occurs

Scheme 690

Scheme 692

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smoothly in the presence of aromatic and hydroxyl groups in the substrates.1927 Catalytic NBS can mediate the ring expansion reaction of epoxides under microwave conditions, leading to the formation of cyclic carbonates.1928 Ring opening of the benzylidene acetals of sugars with NBS was carried out by Hanessian.1929−1933 For example, during the course of a reaction, methyl 4,6-O-benzylidene-α-D -galactopyranoside afforded methyl 4-O-6-bromo-6-deoxy-α-D-galactopyranoside, catalytic debenzoylation of which produced methyl 6-bromo-6-deoxy-α1929 D-galactopyranoside. He showed that appropriately substituted methyl 4,6-O-benzylidenehexopyranosides result in the formation of th ecorresponding methyl 4-O-benzoyl-6-bromo6-deoxyhexopyranosides (Scheme 696).1930−1933 The reaction is generally carried out using benzylidene acetal with NBS in refluxing carbon tetrachloride in the presence of barium carbonate (Scheme 696). In those cases where the starting acetals are insoluble in hot carbon tetrachloride or benzene,

Cyclopropylcarbinols were efficiently subjected to ringopening reaction to form 3-(bromomethyl)cycloalkanones by using NBS in t-BuOH at 30 °C (or 60 °C). The product yield was recorded to be 40−60%.1937 Ionic liquids such as [C5Py][Br]1938 and [Acmin][Br]1939 have been reported to be very effective for such ring-opening processes. Xu et al. reported the use of [C5Py][Br] along with CF3COOH or CF3SO3H as a hydrobrominating ionic liquid reagent which helps in the ring-opening reaction of cyclopropyl ketones to the corresponding 3-bromopropyl ketones.1938 [Acmin][Br] was also found to be suitable for the synthesis of vic-bromohydrins from the corresponding epoxides.1939 Recently, Yeung reported Scheme 696

the ring opening of 2,3-dihydrofuran at the C-4−C-5 bond in the presence of the DABCO catalyst and NBS as the electrophilic halogen source. The moisture present in the solvent plays an important role in opening the ring.1940 NBS has been suitably treated in HF/pyridine to synthesize difluoroalkyl ethers from S,S,O-orthoesters.1941

Scheme 693

12. SUBSTITUTION REACTIONS 12.1. Substitution Reactions Using Molecular Bromine

Liquid bromine can be used for various bromo substitution reactions. It can undergo the Hunsdicker reaction,1942,1943 which is a reaction of silver salts of carboxylic acids with halogens to give organic halides. Various types of alkyl bromides can be prepared by the reaction of equal molar amounts of bromine with the silver salts of carboxylic acids. The reaction of bromine with the silver salts of benzoic, ochlorobenzoic, and m-nitrobenzoic acids yields the expected aryl bromides in good yield. The reaction of bromine with silver m-toluate yields 3,4-dibromotoluene in addition to the expected m-bromotoluene, whereas silver m-methoxybenzoate yields mainly 2-bromo-5-methoxybenzoic acid (Scheme 698).1944 Sakefllarios described a method for the replacement of the SO3H and CO2H groups by bromine. When 4-hydroxy-5-

addition of dry tetrachloroethane was necessary to solubilize the substrates. Similar ring opening of 4,6-O-benzylidene acetals of carbohydrates with NBS was also successfully carried out by Chretien and co-workers by using CaCO3 in place of BaCO3.1934 This procedure is successfully applied to a number of highly functionalized substrates without side reactions. Thus, benzylidene acetal was treated with NBS in CCl4 in the presence of CaCO3 to give 90% methyl benzoylbromodeoxyditosylglucopyranoside. Epoxides and aziridines undergo ring opening efficiently with BDMS at room temperature to form the corresponding β-bromohydrins and β-bromo amines, respectively. The conversions are highly regioselective and Scheme 694

Scheme 697

afford the products in excellent yields within a short period of time.1935 NBS was effectively utilized for the ring-opening reaction of 1,2-cyclopropanecarboxylate during a stereoselective synthesis of (S)-(−)-longianone. Bromonium ion-mediated electrophilic ring opening of the cyclopropane ring with NBS in dioxane/water (2:1) produced the bromohydrin in 66% yield (Scheme 697).1936

nitrobenzene-1,3-disulfonic acid or, better, its K salt was treated with 1 mol equiv of bromine in water, the reaction quantitatively produced 2-nitro-6-bromophenol-4-sulfonic acid (or its potassium salt), which with a second mole of bromine produced 2,4-dibromo-6-nitrophenol (Scheme 699), which on further treatment with concentrated HNO3 produced 2-bromo4,6-dinitrophenol.1945 Again, Heller et al. studied the action of bromine on naphthylamine- and aminonaphtholsulfonic acids. For example, 1,4-, 1,5-, and 1,8-aminonaphthalenesulfonic acid reacted with an excess of bromine, yielding the corresponding 2,4-dibromo derivatives, while the 2,5-, 2,6-, and 2,7compounds gave the 1-bromo derivatives.1946 Bromotrimethylsilane was prepared by Palomo and Aizpurua by treating hexamethyldisiloxane with bromine in the presence

Scheme 695

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of PPh3 in 96% yield.1947 The combination of zirconocenemediated coupling of silylated alkynes with a protonation− desilylation or bromination−desilylation process afforded butadienes. For example, when (E,E)-2,3-dialkyl-1,4-bis(trimethylsilyl)-1,3-butadienes were treated with an excess of Br2, (E)2,3-dialkyl-1,1,4,4-tetrabromo-2-butenes were obtained in excellent yields with perfect stereoselectivity (Scheme 700).1948 Jiaet al. reported another bromination−desilylation process of the osmabenzyne complex, where electrophilic substitution of the trimethylsilyl group takes place under the action of bromine.1949 In this reaction, a solution of metallabenzyne [Os(CC(SiMe3)C(CH3)C(SiMe3)CHCl2(PPh3)2] in dichloromethane was treated with an excess of bromine at room temperature for 20 min to produce the bromodesilylated product (Scheme 701). The same group later extended their studies on the action of bromine on different metallabenzynes to afford the corresponding brominated products.1950 Jastrzebski et al. synthesized the polybromo derivative of acetophenone.1951 For example, on treatment of o-dichlor-

Scheme 700

until evolution of HBr ceased to yield 78% 2-bromonaphthalene (Scheme 705).1955 Similarly, using the same procedure, cinnamyl alcohol can be converted to cinnamyl bromide.1956 Certain substituted bromobenzenes have been synthesized in acceptable yields using a Sandmeyer-type reaction with molecular bromine. The reactions are relatively quick and possibly proceed via a radical mechanism (Scheme 706).1957 The reaction of bromine with nickel(II) acetylacetonate led to the oxidative decomposition of the chelate and formation of NiBr3 and 3-bromoacetylacetone.1958 The reaction of the three Scheme 701

Scheme 698

isomeric tributylboranes (tributyl, triisobutyl, and tri-sec-butyl) with bromine in the dark gives rise to both butyl bromide and hydrogen bromide in CCl4.1959 When 1,3,5-tri-tert-butylbenzene was treated with slow addition of bromine in the presence of SbCl3 in dichloromethane, at 5 °C, 1-bromo-3,5-di-tertScheme 702 obenzene with chloroacetyl chloride in the presence of AlCl3, ω,3,4-trichloroacetophenone was obtained, which on treatment with Br2 was converted into ω-bromo-3,4-dichloroacetophenone (Scheme 702). The compound 5-bromopentanoyl bromide was synthesized in a three-step reaction sequence. In the last step, 5bromovaleric acid was allowed to react with bromine in

butylbenzene was obtained after 3 h of reaction (Scheme 707).1960 In the process for the preparation of hydroxydibenzofurans, Tashiro et al. treated biphenyl with bromine in alcohol to give dibenzofurans. They carried out the reaction of 2,2′-dihydroxy3,3′,5,5′-tetra-tert-butylbiphenyl with excess bromine in alco-

Scheme 699

Scheme 703 dichloromethane in the presence of triphenylphosphine at about 0 °C for 1−2 h to produce the final product (Scheme 703).1952 Phenyl bromoacetate was prepared by treatment of acetic acid with thionyl chloride, bromination with bromine, and treatment with phenol or PhONa. The yield of the product was found to be greater than 90%.1953 Takaya and co-workers synthesized (R)-(+)- and (S)-(−)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl. In the first step of the synthesis, dihydroxybinaphthyl was reacted with triphenylphosphine and bromine in acetonitrile followed by heating to 310−320 °C to obtain 2,2′-dibromo-1,1′-binaphthyl (Scheme 704).1954 Further reaction with 2,2′-dibromo-1,1′-binaphthyl led to the final product. β-Naphthol was heated at 60−70 °C with Ph3P·Br2 in MeCN and then, after evaporation of the solvent, heated to 340 °C

hols to produce the 2-alkoxy-1-bromo-4,6,8-tri-tert-butyldibenzofurans (Scheme 708).1961 However, at room temperature, this reaction afforded 1-bromo-2-methoxy-4-tert-butyldibenzofuran. Stepanov et al.1962 described that bromine reacts rapidly with paraldehyde with the formation of a mixture of bromination products from which the pure monobromoparaldehyde can be isolated in 50% yield. With 2 mol of bromine, dibromoparaldehyde was obtained with a considerable amount of tribromo product. With 3 mol of Br, the reaction was more complicated; decolorization does not take place even after 3 days, and at the end of the second day only a mixture of di- and tribromo 6964


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Scheme 704

Scheme 708

compounds was obtained. Bromination of substituted ethylarylarsines, ArRAsEt (R = p-tolyl, NEt2, t-BuO), with bromine in benzene affords ArRAsBr with substitution of the ethyl group with bromine.1963 When R is another ethyl group, consecutive bromination occurs, with the formation of both REtAsBr and

Another process for the preparation of 1,4-dibromotetrá fluorobenzene was developed by Nikulshin and co-workers.1968 The reaction proceeds through substitution of the thiol group by bromine, which was achieved by the pyrolysis of 4bromotetrafluorobenzenethiol with Br2 at 400 °C (Scheme 711). Yang et al. described the preparation of 1-amino-4bromoanthraquinone-2-sulfonic acid sodium salt where Br2 was used as the brominating agent.1969 First, 1-aminoanthraquinone was sulfonated with fuming H2SO4 at 100− 140 °C to obtain 1-aminoanthraquinone-2,4-disulfonic acid,

Scheme 705

RAsBr2. 2,2-Dibromo-2-nitroethanol was produced by Iwabuchi et al.1964 in both high yield and high purity by the reaction of an aqueous solution of tris(hydroxymethyl)nitromethane with an

Scheme 709

Scheme 706

which was then desulfonated with 70−100% H2SO4 at 60−150 °C for 1−5 h. Finally, it was brominated with Br2 at 60−90 °C (Scheme 712). 1,1-Dinitro-3-chloromercuripropane, on treatment with bromine in carbon tetrachloride under reflux conditions for 3 days in the presence of a trace of benzoyl peroxide, gave 76% 3bromo-1,1-dinitropropane (Scheme 713). 1,1-Dinitro-2-methyl-3-(chloromercurio)propane, under similar conditions, produced 90% 1-bromo-2-methyl-3,3-dinitropropane. Similarly, 1bromo-2-phenyl-3,3-dinitropropane, 1-(dinitromethyl)-2-bromocyclopentane, and 1-(dinitromethyl)-2-bromocyclohexane were obtained in 87−91% yield.1970 Ruano revealed that lithium o-sulfinylbenzyl carbanions are highly efficient reagents for the synthesis of optically pure benzylstannanes by reaction with halotriorganyltin.1971 They found that bromolysis of the obtained (o-sulfinylbenzyl) stannanes with bromine in the presence of cupric bromide took place in a highly stereoselective way with retention of the configuration. This led them to synthesize optically pure 2sulfinylated benzyl bromides in an efficient manner (Scheme 714).

aqueous alkali solution at room temperature, followed by reaction of the intermediate with Br2 (Scheme 709). Perfluoroalkyl iodides and perfluoroalkylene diiodides were converted to perfluoroalkyl bromides and perfluoroalkylene dibromides by gas-phase reaction with bromine as a brominating agent.1965 Bobyleva et al. treated 4-endo-8-exodiiodobrexane with Br2 and CH2Cl2 at room temperature to produce a mixture of 2(R),4(S)- and 2(R),4(R)-dibromobrendane in a 1.5:1 proportion and 98% yield.1966 The same reaction at −23 °C afforded a mixture of four isomers, namely, Scheme 707

Scheme 710

4-endo-iodo-8-exo-bromo- and 4-endo-iodo-8-endo-bromobrexane and 4-exo-8-exo-dibromo- and 4-exo-8-endo-dibromobrexane in a 4:12:1:3 proportion. They also studied the reaction of 4-endo-iodo-8-brexene with (p-tolylsulfonyl)hydrazine and triethylamine in diglyme to produce a 68% yield of 4-endoiodobrexane, which on subsequent treatment with bromine in carbon tetrachloride produced 2-exo-bromobrendane in 96% yield. Askham developed a procedure for the conversion of hexafluorobenzene to bromopentafluorobenzene using bromine. The process involves the reaction of hexafluorobenzene with ethylmagnesium bromide in the presence of a catalytic amount of FeCl2 to form pentafluorobenzene magnesium bromide, which was then brominated with bromine in CH2Cl2 to produce bromopentafluorobenzene (Scheme 710).1967

12.2. NBS-Mediated Substitution Reactions

The reaction of alkenylboronic acids, such as (E)-(2-phenylvinyl)boronic acid, with NBS gives the corresponding alkenyl bromide with the same geometry (Scheme 715).1972 The reactions were carried out by reacting alkenyl boronic acids with NBS in acetonitrile at room temperature. This method is 6965


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Scheme 711

Scheme 715

suitable for the synthesis of geometrically pure (E)- and (Z) alkenyl halides, as well as 1,1- and 1,2-dihaloalkenes. Aryl- and heteroarylboronic acids react with NBS in acetonitrile at reflux temperature to give the corresponding bromoarenes in good to excellent yields (Scheme 716).1973 The reaction is highly regioselective and produces only the ipsosubstituted product. Esters of arylboronic acids react similarly, but the reaction is much slower in this case.

propiolic acids with NBS at ambient temperature in the presence of 10 mol % TBATFA produced the 1-bromoacetylenes in high yield. Roy also successfully used Mn(OAc)2, quaternary ammonium salts, and NEt3 as the catalyst in Hunsdiecker reactions.1981−1983 Various cinnamic acids and propiolic acids are converted to the corresponding α-bromostyrenes and 1bromo-1-alkynes by treatment with NBS in the presence of 5 mol % NEt3 at room temperature in good isolated yields within 1−5 min.1983 Wilt and Diebold prepared dibromoacetonitrile

Scheme 712

Scheme 716

from cyanoacetic acid using NBS.1984 The reactions were carried out with cyanoacetic acid and NBS in cold water as the reaction medium at room temperature in a short time period (Scheme 719). Janz and Kaila presented a procedure for the bromodecarboxylation of quinolinesalicylic acids.1985 The reaction was carried out by treating the precursor acid with NBS in THF at room temperature to furnish the product in high yield (Scheme 720).

(E)-β-Arylvinyl bromides were synthesized from styrenes via a highly selective Ru-catalyzed silylative coupling−bromodesilylation process. The bromodesilylation process was carried out by using NBS (1.2 equiv) in acetonitrile/water (4:1) at room

Scheme 717

Scheme 713

NBS is also found to be a suitable reagent for the substitution of the hydroxyl functionality with bromine.1986−1989 Though the substitution process is very effective in the presence of PPh3,1986−1988 phosphorus reagent free methods1989 are also available for the same process. Murakami et al. described a onepot synthesis of aryl sulfones from primary alcohols.1988 In this method alcohols were treated with NBS and triphenylphosphine, followed by the addition of sodium arenesulfinate with a catalytic amount of tetrabutylammonium iodide to afford the aryl sulfones in good to high yields (Scheme 721). Thomas et al. used NBS for the conversion of the hydroxymethyl group to the corresponding bromomethyl compound.1990 They carried out the reaction with NBS in the presence of PPh3 in THF. The bromomethyl compound was used for further elaboration to the dendrons (Scheme 722). A combination of NBS and tetrabutylammonium triflate (Bu4NOTf) or diphenyliodonium triflate (Ph2IOTf) effectively activates thioglycosides to promote glycosidation with various glycosyl acceptors.1991 NBS is also a suitable reagent for substitution of the thio group.1992 Fukaseet al. reported a stereoselective glycosidation with thioglycosides by the

temperature.1974−1976 Vinyl halides can also be synthesized via a bromodealumination process by using NBS.1977 Chowdhury and Roy carried out LiOAc-catalyzed halodecarboxylation of α,β-unsaturated carboxylic acids to bromoalkenes with NBS (Scheme 717).1978 In this reaction, the α,β-unsaturated carboxylic acids were added to a solution of LiOAc in an acetonitrile and water mixture in the presence of NBS at room temperature to obtain the desired bromoalkene. Kuang et al. improved the reaction time (1−2 min) of the LiOAc-catalyzed halodecarboxylation reaction with the help of microwave irradiation in the presence of NBS.1979 They observed the formation of cis-α-bromo-β-lactone when the reaction was carried out with cis-cinnamic acid and NBS, which provided a useful support for the mechanistic study of the present halodecarboxylation reaction. Again, Roy et al. prepared 1-bromoalkynes from propiolic acids using a catalytic decarboxylation protocol in the presence of tetrabutylammonium trifluoroacetate (TBATFA) as the catalyst (Scheme 718).1980 For example, the reaction of substituted phenylScheme 714

Scheme 718

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combined use of NBS and a catalytic amount of various strong acid salts (Scheme 723).1993A combination of NBS with Ph2IOTf, Bu4NOTf, or Bu4NCIO4 was found to be advantageous for β-selective glucosidation with 2-O-acylated or 2-Obenzylated donors by virtue of either the neighboring group participation or the known solvent effect of nitrile, respectively.

Scheme 723

Scheme 719

Lin has carried out the scope of the abnormal bromination of α-cyclocitral with NBS.1994 From the reaction of α-cyclogeranic acid with NBS, 1,1,3-trimethyl-2-bromo-3-cyclohexene and 1,1,3-trimethyl-2,5-dibromo-3-cyclohexene were obtained as the products (Scheme 724). It was concluded that a bromine

12.3. Substitution Reactions with Other Bromo-Organic Compounds

Madhusudan and Misra reported the facile conversion of glycosyl S,S-acetals to their corresponding O,O-acetals using DBH (Scheme 726).1999 They achieved the transformation by treating the glycosyl S,S-acetals with DBH in anhydrous methanol at 0 °C to obtain the corresponding O,O-acetals.

Scheme 720

Scheme 724

atom replaces the H atom on the tertiary carbon atom in αcyclogeranic acid, and then, because of the lower stability of the tertiary carboxylic acid, decarboxylation occurs. The rapid synthesis of 3,4-substituted indoles via a directed ortho metalation−retro-Mannich sequence was presented by Chauder et al.1995 In the test experiment of the retro-Mannich fragmentation, N-(triisopropylsilyl)gramine, when subjected to NBS, afforded, within minutes, the 3-bromo derivative in essentially quantitative yield (Scheme 725).

2,4,4,6-Tetrabromocyclohexa-2, 5-dienone was also successfully used in the nucleophilic substitution of bromine for hydroxyl; i.e., it served as a source of nucleophilic halogen in the presence of triphenylphosphine (Scheme 727).2000 This reaction was performed with primary, secondary, sterically hindered, and cage alcohols to give high yields of the corresponding bromides. This reagent was found to be regiospecific, which was demonstrated for the replacement of the hydroxyl group in secondary and especially in branched


Chiral allylic sulfinyl alcohols on treatment with NBS/Me2S are transformed into the rearranged primary allylic bromides via an SN2′ displacement reaction, which in the presence of KOH/ i-PrOH at −20 °C produced optically pure (R)- and (S)-2-(ptolylsulfinyl)-1,3-alkadienes via E2′ eliminations.1996 Bennett et

secondary alcohols. The high regio- and stereospecificity of the reagent was also shown for alcohols such as analogues of natural carbinols. Furukawa et al. used BDMS for the preparation of alkyl bromide from the corresponding alcohol. The yields were very good. The reaction proceeds via an inversion; i.e., an optically active alcohol gives the corresponding bromide with inversion of configuration.2001 Yazima and Munakata used PBr3 as the brominating agent in combination with DMF for the synthesis of 2- and 4- bromoquinolines from the corresponding methoxyquinolines (Scheme 728).2002 They reported that the reagent could be used under mild conditions and it was useful in brominating complex molecules. They observed that by using this reagent the methoxy groups attached at the 2- and 4-positions of the quinoline ring could be readily replaced by bromine atoms. The structure of the reagent was not clear,but they assumed that it might be an iminium salt. Wang et al. reported the process for the preparation of transresveratrol. In the first step, 4-(benzyloxy)benzyl alcohol was brominated with boron tribromide to obtain 4-(benzyloxy)

Scheme 722

al. also adopted a similar methodology for the synthesis of methyl (Z)-2-(bromomethyl)-4-methylpent-2-enoate from methyl 3-hydroxy-4-methyl-2-methylenepentanoate.1997 Carbohydrate derivatives were also suitably substituted by Br at C-1 and C-5 (or C-4 in furanoid derivatives) hydrogens by using NBS in the presence of the radical initiator Bz2O2 under reflux conditions in CCl4. The regioselectivity of the transformation depends largely on the substituents at C-1 and C-5.1998 6967


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benzyl bromide.2003 (Tribromomethyl)arenes were prepared efficiently by Chen et al. at room temperature from

the reactions of the 4-tert-butylcyclohexene trans-diaxial bromohydrins with SOBr 2 and SOBr 2 −pyridine. 2008 Br3CCOCBr3 in combination with PPh3 can be utilized for the bromination of alcohols.2009,2010 Tongkate et al. carried out the bromination of a variety of alcohol to the corresponding alkyl bromides utilizing Br3CCOCBr3/PPh3 as the brominating agent (Scheme 731).2009 The yields were very high under mild conditions with short reaction times. All the primary and secondary alkyl and cyclic alcohols studied were converted into the corresponding alkyl bromides in high yields using this reagent. An olefinic byproduct was also detected as a minor component. A series of benzyl bromides were efficiently prepared from the corresponding alcohols with Br3CCOCBr3/PPh3 at low temperature and under neutral conditions by Joseph et al. (Scheme 732).2010 Recently, the DBH/PPh3 combination was utilized for the bromination of benzylic alcohols.2011 Using THF as the solvent, dibromination of benzylic diols was conducted in moderate to good yields for a wide variety of electron-deficient, electronneutral, and electron-rich aromatic substrates. Mase et al. has

Scheme 726

(trifluoromethyl)arenes with boron tribromide as the brominating reagent. The process was applicable to the preparation of various substituted benzotribromide derivatives from substituted benzotrifluoride compounds.2004 Pelletier and Poirier Scheme 727

used boron tribromide as brominating agents for the conversion of alcohol to bromide (Scheme 729). At first they observed that 16α-(hydroxyalkylamido)-3-methylestradiol was converted to 16α-(bromoalkylamido)estradiol by boron tribromide. Encouraged by this result, they examined the reaction with BBr3 to various kinds of alcohols (tertiary, secondary, primary). Symmetrical cyclohexanol was found to be inactive, and hindered secondary alcohols and primary alcohols showed a very low reactivity.2005 Waldman et al. presented an improved synthesis of a potent serotonin agonist, (aminopropyl)methoxybenzofuran, and its novel derivatives. The synthesis included an unusual, one-pot demethylation/primary alcohol bromination with boron tribromide.2006 The reaction was carried out with BBr3 in a

Scheme 730

carried out the bromination of hydroxyheteroarenes using P2O5/Bu4NBr under mild reaction conditions to afford high yields of various bromoheteroarenes.2012 The procedure was successfully applied to large-scale syntheses of bromoheteroarenes (Scheme 733). Tetrabutylammonium tribromide (TBATB) was found to be a bromodeboronation reagent for organotrifluoroborates.2013,2014 Aryl, alkenyl, and alkynyl trifluoroborates bearing a wide range of functional groups can be converted to the corresponding bromo derivative with excellent yields (Scheme 734). The method is highly regio- and chemoselective in the presence of both unsaturated carbon−carbon bonds and aldehyde functional groups. Cyanogen bromide was successfully utilized in the amine dedialkylation process by using 2-(piperidin-1-yl)acetic acid derivatives.2015 The reaction was carried out in dichloro-

Scheme 728

dichloromethane medium at a temperature ranging from −78 °C to room temperature for 22 h (Scheme 730). 4-(Bromomethyl)benzal bromide and 1,4-bis(dibromomethyl)benzene were prepared in 80% and quantitative yields, respectively, by treating 4-methylbenzaldehyde or terephthalaldehyde with thionyl bromide at 100−120 °C for 2−2.5 h.2007 Thionyl bromide can be used as a brominating agent for various kinds of conversions. For example, Bellucci et al. investigated the conversion of (S)-(−)-2-bromo-1-butanol into 1,2dibromobutane with SOBr2 and SOBr2−pyridine. Again, equilibrated mixtures of trans-dibromides were obtained in

Scheme 731

methane at room temperature for 48 h to produce the 2-aryl-2bromoacetic acid derivatives (Scheme 735).

Scheme 729

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Ohe has shown a method where the direct cyanation reaction of aromatic and heteroaromatic C−H bonds was carried out using cyanogen bromide in the presence of GaCl3 (10 mol %) in dichloroethane at 120 °C (Scheme 736).2016

Scheme 735

Scheme 732

Ionic liquids such as [bmin][Br], [Primin][Br], [Hmin][Br], [omin][Br], and [pmin][Br] are also found as suitable brominating reagents for the synthesis of alkyl bromides from alcohols.2017−2021

Scheme 736

13. PROTECTION AND DEPROTECTION REACTIONS A method for the acetylation of a variety of alcohols was reported by Karimi and co-workers in good to excellent yields with acetic anhydride in the presence of NBS.2022 The reaction was carried out by treating the alcohol with acetic anhydride in

Aldehydes react with Ac2O in the presence of a catalytic amount of NBS to provide the corresponding 1,1-diacetates (gem-diacetates) in good to excellent yields.2027 More protocols were developed to protect alcohols in the presence of NBS.2028,2029 A variety of alcohols were acetylated in good to excellent yields with Ac2O in the presence of catalytic NBS in CH2Cl2 at room temperature. The reactions are clean, and in almost all cases no detectable byproduct was observed.2028 Hajipour and co-workers have carried out a chemoselective, straightforward, and rapid method for the thioacetalization of aldehydes by the use of 1,2-ethanedithiol and a catalytic

Scheme 733

the presence of a catalytic amount of NBS in CH2Cl2 at room temperature to produce the acetylated product in high yield (Scheme 737). This method was further utilized by Sun et al. for the acetylation of sugar cane bagasse.2023 They also found that the modification of native sugar cane bagasse hemicelluloses with succinic anhydride can be carried out using NBS as a catalyst in N,N-dimethylacetamide in the presence of lithium chloride.2024

Scheme 737

amount of NBS under solvent-free conditions. The reaction takes place in excellent yields and short reaction times.2028,2029 NBS was reported to catalyze highly chemoselective acetalization of carbonyl compounds using 1,3-propanediol, silylated diols, and pentaerythritol under neutral conditions.2030,2031 An efficient and high-yielding method for the acylation of alcohols with acetic anhydride using DBH has been reported.2032 N,NDibromo-p-toluenesulfonimide efficiently catalyzes the acylation of structurally diverse alcohols by the action of acetic anhydride in dichloromethane at room temperature.2033 This reaction has been investigated with different types of alcohols, including primary (acyclic and benzylic), secondary (acyclic, cyclic, and benzylic), and sterically hindered tertiary alcohols. Various alcohols and phenols, amines, and thiols and thiophenols have been transformed easily to the corresponding acetate derivatives on treatment with 2 equiv of acetic anhydride in the presence of 5 mol % BDMS precatalyst at room temperature in good yields. In addition, various aldehydes have also been converted to the corresponding gem-diacetates in good yields by employing a 10 mol % concentration of the same precatalyst using 4 equiv of acetic anhydride.2034 A wide variety of carbonyl compounds were converted smoothly to the corresponding acetals on treatment with alcohols or diols and triethyl orthoformate in the presence of a catalytic amount of BDMS at room temperature.2035 Similarly, various carbonyl compounds were transformed into the corresponding dithioacetals on reaction with thiol or dithiols at room temperature by employing the same catalyst, without any solvent (Scheme 738). Moreover, O,O-acetals were converted into the corresponding dithioacetals under identical conditions.

Scheme 734

Karimi also reported the use of NBS for the acetalization of carbonyl compounds.2025 Various types of carbonyl compounds were converted to the corresponding diacetates in the presence of NBS under almost neutral reaction conditions. Due to the neutrality of the medium, this method is especially useful for the protection of acid-sensitive substrates. Similarly, the treatment of 1-acylimidazoles with alcohols in the presence of NBS led to the rapid formation of the corresponding esters. The carboxylic acids with less than two hydrogen atoms at their α-positions generally gave good results. Hindered esters such as tert-butyl pivalate could be prepared by this procedure.2026 6969


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Many primary, secondary, and tertiary alcohols and phenolic hydroxyl groups were effectively converted to their corresponding trimethylsilyl ethers using hexamethyldisilazane in the presence of a catalytic amount of tribromoisocyanuric acid and DABCO−bromine under mild conditions at room temperature with short reaction times in good to excellent yields.2036 Excellent chemoselective silylation of hydroxyl groups in the presence of other functional groups was also observed. Thus, tribromoisocyanuric acid-catalyzed trimethylsilylation of PhCH 2 OH with hexamethyldisilazane gave 100% PhCH2OSiMe3 at room temperature. Poly(N-bromobenzene1,3-disulfonamide) (PBBS) and N,N,N′,N′-tetrabromobenzene-1,3-disulfonamide (TBBDA) were reported as efficient catalysts for the silylation of alcohols, phenols, and thiols in the presence of HMDS under various conditions (Scheme 739). Since there are few reports on the silylation of thiols in the literature, the method is suitable and practical for this purpose.2037 DBH efficiently enhances the rate of trimethylsilylation of different types of alcohols with HMDS.2038 Alcohols were also converted to their corresponding tetrahydropyranyl (THP) ethers with 3,4-dihydro-2H-pyran in the presence of DBH. The method is mild, and the products were obtained in high yields. This reagent was also used for the selective trimethylsilylation or tetrahydropyranylation of various types of alcohols in the presence of tertiary alcohols. The application of 1,3-dibromo5,5-diethylbarbituric acid as a catalyst was described in the

Scheme 739

presence of 3 mol % BDMS at 0−5 °C.2045 Similarly, dipropyl dithioacetal derivatives were also obtained in good yields using propanethiol under identical reaction conditions. Ding et al. reported 4,6-O-benzylidenation of D-galactal with 1-(dimethoxymethyl)benzene using BDMS as the catalyst.2046 Methyl 2dexoy-4,6-O-benzylidenegalactopyranoside was prepared efficiently by treating the corresponding D -galactal with Scheme 740

PhCH(OCH3)2 in the presence of a catalytic amount of BDMS in acetonitrile (Scheme 742). Various O-isopropylidene derivatives of sugars and acyclic sugars were obtained in very good yields on reaction with acetone at room temperature with a catalytic amount of BDMS (Scheme 743).2047 The reaction was carried out with a solution of sugar in dry acetone or in a mixture of dry acetonitrile and 2,2-dimethoxypropane using BDMS at room temperature to give the O-isopropylidene. A variety of aldehydes and ketones were converted easily to the corresponding 1,3-oxathiolane derivatives on treatment with 2-mercaptoethanol using a catalytic amount of BDMS as the precatalyst at room temperature under solvent-free

Scheme 738

Scheme 741 protection of different alcohols by HMDS in good to high yields in the absence of solvent at room temperature.2039 A good selectivity was observed for the protection of alcohols over phenols. NBS was found to be an efficient catalyst for the trimethylsilylation of alcohols using HMDS2040 (Scheme 740). However, this reaction is effective only under solvent-free conditions at 50 °C. Various alcohols and phenols could be converted efficiently to the corresponding tetrahydropyranyl (THP) ethers in good yields using catalytic amount of BDMS (0.005−0.02 equiv) at room temperature.2041 Various THP ethers were also deprotected to the parent alcohol or phenolic compounds in CH2Cl2/MeOH (5:2) by employing 0.05 equiv of the same catalyst. N,N′-Dibromo-N,N′-1,2-ethanediylbis(ptoluenesulfonamide) (BNBTS) has catalytically been applied for the tetrahydropyranylation of a wide range of alcohols and phenols in dichloromethane, and tetrahydropyranylation of these compounds has also been carried out in methanol at room temperature (Scheme 741).2042 A protocol for the protection of aryl and aliphatic amines with tert-butoxycarbonyl (t-Boc) and (benzyloxy)carbonyl (Cbz) catalyzed by BDMS was developed by Shailaja et al.2043,2044 Rapid protection of amines was achieved in excellent yields under solvent-free conditions. A variety of diethyl dithioacetals of sugars were prepared in very good yields by the reaction of various monosaccharides with ethanethiol in the

conditions.2048 Similarly, both aromatic and aliphatic aldehydes have been converted to their corresponding oxathioacetals (Scheme 744), thioacetals, and dithioacetals employing NBS as a catalyst.2049 The protection of aldehydes was carried out by treatment with 2-mercaptoethanol, thiol, or dithiol in the presence of 30 mol % NBS in dichloromethane at room temperature. High chemoselectivity and yields were observed within a short reaction time. Various types of carbonyl compounds were efficiently converted to their 1,3-dioxanes and pentaerythritol diacetals by the use of either 1,3-bis(trimethylsiloxy)propane or 1,3bis[(trimethylsilanyl)oxy]-2,2-bis[[(trimethylsilanyl)oxy]methyl]propane and a catalytic amount of NBS (3−10 mol %) in DCM (Scheme 745). A variety of functionalities such as both aliphatic and phenolic −O(TBDMS), −OMe, −OBz, the furan ring, double bonds, and more significantly phenolic −O(THP) survived under the present reaction conditions. The efficient conversion of two α-tertiary ketones to their cyclic acetals was also achieved using the present protocol. 6970


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debenzylation may involve an oxygen/light-initiated free radical mechanism. Various types of 1,3-oxathiolanes of aromatic and aliphatic carbonyl compounds, including those obtained from α,β-

Scheme 742


unsaturated aldehydes, were efficiently converted to the corresponding carbonyl compounds in the presence of NBS (0.4−0.9 equiv).2058 The method was also effectively applied

A catalytic amount of BDMS or Nafion-H along with NaI (1 equiv) in methanol cleaves a variety of tert-butyldimethylsilyl (TBDMS) ethers readily in high yields. Alkyl TBDMS ethers react more readily and selectively compared to phenolic TBDMS ethers and benzyl and methyl ethers.2050 NBS was used for the oxidative deprotection of TBDMS ethers. Treatment of TBDMS ethers with NBS in the presence of βcyclodextrin in water resulted in the cleavage of the silicon− oxygen bond. The carbonyl compounds are obtained upon oxidation.2051 Conversion of 1,1-diacetates to aldehydes has

Scheme 747

Scheme 744 for the chemoselective deprotection of 1,3-oxathiolanes in the presence of 1,3-dioxolanes. Interconversion of a range of 1,3oxathiolanes, 1,3-dithiolanes, and 1,3-dithianes to their acetals at room temperature using NBS and different types of alcohols and diols was studied by Karimi et al. (Scheme 751).2059 The reaction was achieved by using equimolar or a slight excess of NBS in the presence of an alcohol or a diol. The reaction was found to be very fast and goes to completion in 5 min at room temperature. The oxidative method for the hydrolysis of 1,3-dithianes was carried out by Patrocinio and Moran.2060 BNBTS has also been used for the deprotection of aliphatic and aromatic 1,3dithianes to their corresponding carbonyl compounds in the presence of silver nitrate in an acetonitrile medium at room temperature.2061 Treatment of 2-silyl-1,3-dithianes with 4−6 equiv of NBS in aquous acetone or acetonitrile provided acylsilanes with good yields (40−96%) within a short reaction period (Scheme 752). Davis et al. reported that the hydrolysis of sulfimine-derived N-(sulfinylamino)-1,3-dithianes with aqueous DBH affords the corresponding N-tosylamino aldehydes in good yields and with high enantiomeric purity (Scheme 753).2062 Rama Rao and co-workers found a method for the oxidative deprotection of THP ethers with NBS in the presence of βcyclodextrin in water.2063 A series of tetrahydropyranyl ethers were oxidatively deprotected at room temperature in impressive yields. They also reported a method for the oxidative deprotection of tert-butyldimethylsilyl (TBDMS) ethers with NBS in water.2064 Treatment of TBDMS ethers with NBS in the presence of β-cyclodextrin in water resulted in the cleavage of the silicon−oxygen bond. carbonyl compounds are obtained upon oxidation (Scheme 754). Valerio et al. carried out the activation of thio- and selenoglycosides by the NBS/Bi(OTf)3 system (Scheme 755).2065 They disclosed that disarmed thioglycosides could be activated in dichloroethane at temperatures as low as −30 °C by a catalytic amount of Bi(OTf)3 (added as a solution in dioxane).

been described using BNBTS in high yield and a short time at room temperature under solvent-free conditions.2052 NBS also acted as a catalyst when it was applied for the solvent-free deprotection of 1,1-diacetates to the corresponding aldehydes using wet SiO2 as a solid support (Scheme 746).2053 NBS in the presence of methanol can effectively regenerate aldehydes and ketones, in around 74% yield, from the corresponding (p-tolylsulfonyl)hydrazones (Scheme 747).2054 A method was described for the regioselective partial deprotection of carbohydrates protected as benzylidene acetals by Binkley et al. 2055 The deprotection reaction was Scheme 745

accomplished for each of the six methyl pyranosides studied by irradiation of the protected sugar and NBS in the presence of water (Scheme 748). Under these conditions, the benzylidene (1,3-dioxolane) ring in each compound opened to give a methyl pyranoside with an axial benzoyloxy group and an equatorial hydroxy group. Baker et al. carried out the deprotection of N-benzyl amides under neutral conditions by reaction with NBS in chlorobenzene or ethyl acetate in reflux conditions (Scheme 749).2056 Good to excellent yields were obtained using either acyclic or cyclic amides. However, Kuang found that the cleavage of the N-benzyl group on N-mono- or disubstituted carboxamides using NBS can be achieved at room temperature in chloroform as the solvent with excellent deprotection yields (Scheme 750).2057 The investigation of the reaction indicated that the 6971


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Scheme 748

out by using N,N-dibromobenzenesulfonamide.2069 The cleavage experiments were carried out in nonaqueous and aprotic conditions at room temperature to regenerate the parent carbonyl compounds in high yield. The same group also developed similar methods of oxidative cleavage of oximes using N-bromobis(p-tolylsulfonyl)amine2070 and N,N′-dibromo-N,N′-1,3-propylenebis(4-methylbenzenesulfonamide).2071

Scheme 749

Scheme 750


NBSac was found to be an efficient reagent for the oxidative cleavage of oximes to the corresponding aldehydes and ketones.2072,2073 N,N-Dibromo-N,N-1,2-ethanediylbis(p-toluenesulfonamide) [BNBTS] was reacted with oximes to convert them to their corresponding carbonyl compounds in good yields in carbon tetrachloride at room temperature.2074 NBromophthalimide (NBP) has been found to be an efficient and selective reagent for the mild oxidative cleavage of oximes to yield the corresponding carbonyl compounds in good to excellent yields.2075 Similar reactions were also carried out under microwave irradiation in a very short time (Scheme 757).2076 Das et al. used tetra-n-alkylammonium bromates for the deoximation of oximes to the corresponding carbonyl compounds.2077 They prepared tetraalkylammonium bromates from the corresponding bromides by passing chlorine gas through an aqueous NaOH solution. They carried out the deoximation reaction by refluxing the oxime in toluene (Scheme 758). They also used tetraalkyl ammonium bromates for the oxidative regenaration of the parent carbonyl compound from their semicarbazones.2078 Tetraalkylammonium bromates were used as primary oxidants for the oxidative cleavage of >CN− of hydrazone to the carbonyl compounds. The reaction conditions are simple, and the products were obtained in high yields.2079 Beheshtiha et al. carried out the deoximation reaction with the help of molecular bromine.2080 A combination of hexamethylenetetramine and Br2 on alumina rapidly regenerates carbonyl compounds from their corresponding oximes in dry CH2Cl2. For example, a yield of 92% of benzaldehyde was obtained from its oxime in 40 min using this procedure. In another example, 82% propiophenone was regenerated. Deprotection of (2,4dinitrophenyl)hydrazones to their corresponding carbonyl

The conversion of different oximes to the corresponding carbonyl compounds is a well-known reaction. Bandgar reported a method for the selective regeneration of carbonyl compounds from oximes using NBS under mild conditions.2066 Reddy also found that oxidative cleavage of oximes can be Scheme 752

achieved using NBS in water in the presence of β-cyclodextrin at room temperature to generate the corresponding carbonyl compounds (Scheme 756).2067 We also found that TsNBr2 can be used for the oxidative deprotection of oximes to the corresponding carbonyl compounds.2068 Deprotection of different oximes to their parent aldehydes and ketones in high yields has been carried Scheme 753

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Scheme 755

Scheme 756

Scheme 758

compounds has been reported in good yields with BNBTS under microwave irradiation (Scheme 759).2081 Malik and Kartha disclosed a mild, highly efficient, and chemoselective deprotection procedure of trityl ethers of carbohydrates and nucleosides using iodine monobromide.2082 IBr in CH2Cl2−MeOH or MeCN constitutes an effective reagent for the deprotection of o-trityl and o-dimethoxytrityl ethers of carbohydrates and nucleosides. Acid-labile functionalities (acetals, O-4-methoxybenzyl ethers, etc.) as well as baselabile groups (esters and amides) are stable under these conditions. Lewis et al. used Br2 in CCl4 for the conversion of 1,2-bis[(trimethylsilyl)oxy]-3,3,6,6-tetramethylcyclohex-1-ene to cyclic diketone 3,3,6,6-tetramethylcyclohexane-1,2-dione (Scheme 760).2083,2084 This cyclic diketone undergoes cyclocondensation with 2,2′-bipyridine-6,6′-dicarbohydrazonamide to give bispyridine derivatives.

Scheme 759

Scheme 760

(KSCN) to give 50% RCOCH2SCN followed by intramolecular cycloaddition to give 47% thiazole. Further reaction led to 68% benzopyranoquinolinone.2088 A convenient synthesis of 2,4-bis(methylthio)-1-naphthol and 2,4-bis(methylsulfonyl)-1-naphthol was reported by Bereznak et al. In this case, 1-naphthol was treated with KSCN and bromine in the first step of the synthesis.2089 2-Amino-6-(2-naphthalenyl)thiazolo[3,2-d]thiadiazole was prepared by the treatment of KSCN

14. MISCELLANEOUS REACTIONS 14.1. Miscellaneous Reactions Using Molecular Bromine

Esselen and co-workers showed that the benzhydrols, with an NH2 or alkylated NH2 group in the ortho or para position to the hydrol group, were split by the action of bromine into benzaldehyde or its derivatives and a halogenated aniline derivative (Scheme 761).2085 The reactions were carried out by reacting hydrols with bromine in chloroform solution. A one-pot synthesis of 3-[2-(3,4,5-trisubstituted 1H-pyrazol1-yl)-4-thiazolyl]-2H-1-benzopyran-2-ones has been carried out by th condensation of 3,4,5-trisubstituted 1-(thiocarbamoyl) pyrazoles with substituted 3-acetylcoumarins in the presence of bromine in dioxane and DMF on a steam bath.2086 A combination of bromine, triphenylphosphine, and tetrabutylammonium nitrite was used for the preparation of Nnitrosamines and azides from the corresponding amines and hydrazine derivatives, respectively (Scheme 762).2087 The reaction was carried out by treating the precursor amine or hydrazine with the reagent combination Ph3P/Br2/n-Bu4NNO2 in DCM at 0 °C to room temperature. In this reaction, in the first stage, triphenylphosphine reacts with bromine to form the phosphonium bromide. Then addition of n-Bu4NNO2 produces an intermediate and n-Bu4NBr. This intermediate reacts with substrates via substitution at the nitrogen atom. Bromination of RCOMe by Br 2 −AcOH gave 86% RCOCH2Br, which was treated with potassium thiocyanate

Scheme 761

and bromine on 2-amino-4-(2-naphthalenyl)thiazole.2090 For the preparation of 5-amino-3-cyano-4-thiocyano-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]pyrazole as the key intermediate of fipronil, an alcoholic solution of 5-amino-3-cyano1-[2,6-dichloro-4-(trifluoromethyl)phenyl]pyrazole and KSCN was reacted with bromine at 5 °C for 1−5 h.2091 The final product was obtained by pouring the reaction mixture into ice− water and neutralizing it with a Na2CO3 solution. A similar method for the synthesis of 2-amino-5-thiazolyl thiocyanate derivatives was reported, where a solution of 2-amino-5-thiazole was treated with bromine and KSCN in methanol (Scheme 763).2092

Scheme 757

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thiazolidinones (Scheme 766).2102 The conversion was simply

Scheme 762

achieved by treating the substrate with bromine in acetic acid at reflux temperature. Scheme 764 Sain et al. described methods for the synthesis of 4Hpyrimido[2,1-b][1,3]benzothiazole-3-carboxylates and [quinoxalin-2(1H)-ylideneamino]-1,3-benzothiazoles. For this, 4-chloroaniline was converted to 6-chloro-1,3-benzothiazol-2-amine by reaction with KSCN and Br2. This compound acted as a key intermediate for both the series of final compounds.2093 The reactions of N-(methylsulfonyl)- and N-(p-tolylsulfonyl)-2(cyclopent-1-en-1-yl)-6-methylaniline with molecular bromine in the presence of potassium thiocyanate gave N-(methylsulfonyl)- and N-(p-tolylsulfonyl)- 2-(5-isothiocyanatocyclopent-1-en-1-yl)-6-methylanilines.2094 Further reaction of N(methylsulfonyl)-2-(cyclopent-1-en-1-yl)-6-methylaniline with bromine in methanol in the presence of NaHCO3 or with CuBr2 in MeOH afforded N-(methylsulfonyl)-2-(5-methoxycyclopent-1-en-1-yl)-6-methylaniline. The reaction of 3-hydrazino-4,5,6-triphenylpyridazine with different aldehydes gave the corresponding 3-(arylidenehydrazino)pyridazines, which, on reaction with Br2/Na2CO3, gave the corresponding triazinopyridazines.2095 Direct reduction of seven benzoic acids to alcohols via the sodium borohydride−bromine (NaBH4−Br2) reagent was developed by Zhang et al.2096 Tudge et al. carried out the reduction of malonate derivatives using NaBH4 and bromine.2097 In this case, borane−dimethoxyethane generated from the sodium borohydride−bromine mixture efficiently reduces a wide range of malonate derivatives to the corresponding 1,3-diols (Scheme 764).

The Si−C bond in 1-organosilatranes was cleaved by Br2 or ICl to give an 11−42% yield of 1-bromo- or 1-chlorosilatrane, respectively. In the presence of Et2O, THF, or dioxane Scheme 765

dibromide, 1-halosilatranes are formed together with 1-alkoxyand 1-(ω-haloalkoxy)silatranes.2103 Kamata and Tsuge studied the action of bromine on 2,7-dihydro-3,6-diphenyl-1,4,5thiadiazepine.2104When the substrate was treated with bromine in methanol at 0−2 °C, it underwent ring contraction to produce the thiophenes and the thiadiazole (Scheme 767). Subramanyam et al. proposed a method for the polymerization of the acetylenic bond in 2-ethynylpyridines and 2[(trimethylsilyl)ethynyl]pyridine.2105 Formation of a donor− acceptor complex between the pyridine ring in the monomer and bromine provides sufficient activation for the acetylenic triple bond to undergo spontaneous polymerization. The products obtained were substituted polyacetylenes with extensively conjugated backbones, wherein the side group pyridine rings are complexed to bromine in a 1:1 ratio. The polymers were black or brown amorphous solids soluble in polar solvents, indicative of their ionic nature. Iranpoor and coworkers reported a method for the thiocyanation or isothiocyanation of alcohols and protected alcohols. They used bromine and NH4SCN for the conversion of alcohols to their corresponding thiocyanates or isothiocyanates in the presence of 4-aminophenyl diphenylphosphinite (APDPP) as a

Scheme 763

2-[Alkyl(aryl)thio]cyclohexanones were transformed into o[alkyl(aryl)thio]phenols by treatment with bromine or NBS (Scheme 765).2098 The starting ketones were treated with 2 equiv of bromine in chloroform or carbon tetrachioride at 0 °C. Then the reaction mixture was stirred for several hours at room temperature and refluxed if necessary until the reaction was complete. 5-(2-Oxypropyl)-6-azauracil was prepared by irradiating 6azauracil and isoprenyl acetate in a mixture of acetone and water for 2.5 h and dehydrogenating the resulting dihydro-6azauracil by treatment with bromine in water for 10−15 min.2099 The dehydrogenation of various 2,5-diaryl-substituted 2-oxazolines with molecular bromine in the presence of a mixture of LiBr and CaCO3 in refluxing o-dichlorobenzene gives the corresponding oxazole in up to 87% yield. In this case, free radical benzylic bromination followed by dehydrobromination was the expected dehydrogenation pathway.2100 In the synthesis of 4,5-dihydro-6-(4-methoxy-3-methylphenyl)-3(2H)pyridazinones, a mixture of bromine and acetic acid was used as the dehydrogenating agent to produce 6-(4-methoxy-3methylphenyl)-3(2H)-pyridazinone.2101 Omar studied the thioxo to oxo conversion in a variety of 2-thioxo-4-

Scheme 766

heterogeneous and acid scavenger reagent.2106 Yurtanove found that the treatment of diethyl-2-acetamidomalonate with sodium and bromine in absolute ethanol produces tetraethyl 1,2diacetamidoethane-1,1,2,2-tetracarboxylate in 83% yield.2107 It is believed that the reaction proceeds via intermediate formation of an unisolable bromo adduct (Scheme 768). In the synthesis of 2-substituted (4,4,5,5-tetramethyl-2imidazol-1-yl)oxy derivatives, 2-nitropropane was condensed in the presence of sodium hydroxide and bromine to obtain 2,3-dimethyl-2,3-dinitrobutane in the first step (Scheme 769).2108 Gurdere found that the treatment of 1,4-diphenyl-1,4butanedione with bromine produces a mixture of trans-1,26974


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chloride in the presence of NBS. The formation of 1,2-diols via reductive dimerization of aldehydes and ketones in the presence of samarium metal and NBS has been reported by Banik and co-workers.2115 The reaction was carried out by treating the carbonyl compound with NBS in the presence of samarium metal powder in methanol at room temperature (Scheme 773). The carbonyl compounds undergo stereoselective reductive dimerization reactions to give 1,2-diols in 63−79% yields and with 2.3:1−3:1 diastereoselectivities for the DL-diols. Geissman and co-workers reported a procedure for the synthesis of visnaginone using NBS.2116 Initially, they treated the acetate of dihydrovisnaginone with NBS in CCl4 in the presence of a trace of benzoyl peroxide to yield an oily product

Scheme 767

dibenzoylethylene, 2,5-diphenylfuran, 2-bromo-1,4-diphenylbutane-1,4-dione, and cis- and trans-dibenzoyl-1,2-dibromoethane (Scheme 770).2109 14.2. Miscellaneous Reactions Using NBS

Barakat examined the reactivity of NBS with saturated aliphatic dicarboxylic acids such as oxalic acid in an aqueous solution at room temperature.2110 The reaction leads to the evolution of CO2 with the formation of HBr and succinimide. With homologues of the acids, a higher temperature is required for the reaction. The reaction of NBS with unsaturated acids such as maleic and fumaric acids in a boiling aqueous solution produces CO2, HBr, succinimide, and acetaldehyde. Barakat also reported the reaction of NBS with aliphatic α-hydroxy acids to give aldehydes or ketones. The reaction was carried out by refluxing aqueous solution aliphatic α-hydroxy acids with NBS to produce aldehydes or ketones along with carbon dioxide and bromine (Scheme 771).2111

Scheme 771

which was successively treated with dimethylaniline and alcoholic alkali to provide 59% visnaginone (Scheme 774). Δ-2-Pyrazolines were dehydrated to the corresponding pyrazoles by treatment with NBS in CCl4. The rate of reaction

Scheme 768

Scheme 772

2-Arylazirines with NBS in dioxane or carbon tetrachloride at −23 °C afford α,α′-dibromo ketones, dibromoazines, bromopyrazines, 2,5-diarylpyrazines, and 3,6-diarylpyrazines (Scheme 772).2112 Scheme 769

was found to be dependent on the solubility of the pyrazoline in CCl4. For example, dehydration of 3-(p-chlorophenyl)-1-[p[(2-hydroxyethyl)sulfonyl]phenyl]-Δ-2-pyrazoline by this method led to the formation of a 20% yield of 3-(pchlorophenyl)-1-[p-(bromosulfonyl)phenyl]pyrazole as the byproduct along with the dehydrated product.2117 Another interesting reaction of p-bromophenyl benzyl ether with NBS was observed by Braun and Looker.2118 They found that when p-bromophenyl benzyl ether was treated DL-N-[α-(p-bromophenoxy)benzyl]succinimide was formed with good yield (Scheme 775). The reaction was carried out with pbromophenyl benzyl ether using NBS in carbon tetrachloride under reflux conditions. Mancheño et al. used NBS as a halting agent in the synthesis of N-cyanosulfilimines (Scheme 776).2119 It could readily be achieved by the reaction of the corresponding sulfides with cyanogen amine. The reaction was carried out by taking the substrate with cyanogen amine in the presence of t-BuOK and NBS as halogenating agents at room temperature.

Parthasaraty and Rao have developed a one-electron transfer new redox couple, NBS−Fe(II), which was used for the kinetic study of the polymerization of acrylonitrile.2113 The rate of polymerization was found to be dependent on the concentration of acrylonitrile and NBS. Wang and his group have developed a method for the synthesis of imides and acyl sulfonamides via couplings of thioesters with carboxamides or sulfonamides.2114 The reaction was mediated by iron(II) Scheme 770

Scheme 773

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da Silva et al. synthesized 2,2-azopyridine dyes, such as (E)diethyl (diazene-1,2-diyl)bis(5-cyano-2-methyl-4-phenylnicotinate)s, by treatment of ethyl 6-amino-5-cyano-2-methyl-4arylnicotinates with NBS in the presence of benzoyl peroxide in acetonitrile under reflux conditions (Scheme 777).2120

Scheme 776

Scheme 777

Scheme 774

Scheme 778 NBS can mediate the aromatization process. Lokhande has carried out the aromatization and bromination of 3,3a,4,5tetrahydro-3-aryl-2-phenyl-2H-benzo[g]indazole using NBS. Bromination occurs at C-5 of the indazole rings.2121 Carpino et al. synthesized tert-butyl azodiformate from tert-butyl hydrazodiformate by using NBS and an equimolar amount of pyridine in dicholoromethane as the solvent.2122 Alkenes may be synthesized from (α-bromobenzyl)benzyldiphenylphosphonium salts by the action of amine bases. Lawrence et al. synthesized a series of stilbenes by the action of NBS on dibenzyldiphenylphosphonium salts in the presence of 2,2,6,6tetramethylpiperidine in chloroform at room temperature (Scheme 778).2123 Caristi and co-workers reported that N,N-dimethyl amides can be converted to N-succinimidomethyl amides by treatment with NBS in almost quantitative yield.2124 The reaction was carried out in CCl4 in the presence of benzoyl peroxide in reflux conditions (Scheme 779). Gopinath et al. reported an efficient protocol for the synthesis of thioesters from carboxylic acids with the use of acyloxy phosphonium salts as intermediates and benzyltriethylammonium tetrathiomolybdate ([BnEt3N]2MoS4]) as the sulfur transfer reagent.2125 Aryl carboxylic acids were first activated by using PPh3 and NBS to form the corresponding acyloxy phosphonium salts, which then on reaction with the reagent generate thioaroylate ions in situ. These thioaroylates on further reaction with various electrophiles such as alkyl halides/dihalides in the same pot would lead to the corresponding functionalized thioesters (Scheme 780). Chong et al. reported various aziridinium salts from the bromination of a series of backbone-substituted N,Nbisubstituted β-amino alcohols using NBS (Scheme 781).2126 The reaction was carried out by treating the N,N-bisubstituted β-amino alcohol with NBS in the presence of triphenylphosphine initially at 0 °C and continuing the reaction at room temperature. They also studied the effect of C-substitution, Nsubstitution, the solvent, the leaving group etc. Sherry described a method for the synthesis of 2-aminobenzoxazoles from the parent C−H compounds via a 2bromobenzoxazole generated by electrophilic bromination.2127 The procedure involves deprotonation at the 2-position of the banzoxazole with LiHMDS at −20 °C in THF and quenching the intermediate organolithium species with NBS. Subsequent

treatment of the reaction mixture with an amine nucleophile at room temperature afforded the desired product in high yield Scheme 779

(Scheme 782). This process provided a variety of 2-aminobenzoxazoles bearing additional nucleophilic heteroatoms. Ogawa and co-workers found that the reaction of validoxylamine A and its derivatives with NBS results in cleavage of the imino bond.2128,2129 They found that the treatment of vlidoxylamine A with NBS in aqueous DMF produces valienamine, validamine, and cyclohexanone along with some cyclohexenone derivatives. This method could provide an easy route to synthetically and biologically useful valienamine, which was further utilized for the construction of carbaoligosaccharides composed of imino linkages. A method for the stereoselective synthesis of nucleoside derivatives from thioglycosides was developed by Sugimura and co-workers using NBS as the promoter.2130−2133 They achieved the synthesis by coupling thioglycosides with silylated nucleoside bases in the presence of NBS. The reaction proceeds via ion pair intermediates consisting of oxonium ions, derived from thioglycosides, and an imide ion, derived from NBS. In a similar way, they synthesized (2′-deoxy-β-D-threo-pentofuranosyl)pyrimidine nucleosides by coupling phenylidene 2-deoxy-1-thio-αD-threo-pentofuranoside with silylated pyrimidine bases in the presence of NBS in a highly stereoselective manner (Scheme 783). Treatment of various furanosyl and pyranosyl azides with NBS led to the corresponding glycosyl bromo imines in excellent yields (Scheme 784). The reaction was carried out by refluxing a mixture of glycosyl azide and NBS (excess) in

Scheme 775

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Scheme 780

(3H)-ones via a one-pot sequential multicomponent strategy.2137 The final step of this strategy was the aromatization of the intermediate product via a microwave-assisted halogenation−elimination sequence in the presence of NBS (Scheme 786). Breslow and co-workers have carried out the synthesis of 1bromo-3-chloro-2,2-dimethoxypropane from 2,3-dichloro-1propene by using NBS in MeOH at room temperature. Though the process is simple, the yield of the product was found to be low.2138 In a fluorination process during the synthesis of oligosaccharides from phenylthio sugars via glycosyl fluorides, (N,N-dimethylamino)sulfur trifluoride (DAST) was effectively used with NBS.2139 N-Allylhydrazones can also be brominated by using NBS in dichloromethane at 0 °C.2140 Chang et al. used a stoichiometric amount of NBS with chloramine-T at 60 °C in CH3CN for the allylic amination of cyclic olefins,2141 while the catalytic NBS under similar reaction conditions at room temperature provided aziridine compounds.1901 NBS is a very good source for halonium ionmediated cleavage of C−C and N−O bonds in isoxazoline N-

Scheme 781

carbon tetrachloride under the irradiation of a tungsten lamp (250 W). However, peracetylated α-D-glucopyranosyl azide and Scheme 782

the benzyl-protected derivative failed to produce the desired product. The transformation involved primarily the homolysis of activated C−H bonds attached to the anomeric center. O-Glycosides can be synthesized in the presence of NBS.2134,2135 A general procedure for the synthesis of Oglycosides and related acetals with considerable stereocontrol was shown by Nicolaou et al. from phenyl thioglycosides.2134 This method involves the treatment of the readily available phenyl thioglycosides with NBS in the presence of various hydroxy components in organic solvents. The reaction was carried out under anhydrous conditions at 25 °C. Ensley2135 developed the synthesis of O-glycosides with a free C-2 hydroxyl group from thioglycosides through 1,2-acyl group migration, which occurs during the hydrolysis of 4,6benzylidene-protected thioglycosides. The reaction was carried out using 1 equiv of NBS and a catalytic amount of (TMS)OTf (0.1 equiv) at 0 °C in CH2Cl2−H2O (100:1) for 10 min. Protecting groups such as TBS and benzylidene groups survive under the mild reaction conditions. Misra carried out a reaction of glycal derivatives with alcohols/glycosyl acceptors in the presence of NBS and diphenyl diselenide (Scheme 785).2136

Scheme 785

oxides.2142,2143 Recently, Qiu et al. reported a simple, mild, and efficient approach for C−C bond cleavage of β-keto amides using acetic acid as the catalyst to produce α-dibromosubstituted arylamides.2144 N-Alkoxy amides were transformed to carboxylic esters in the presence of NBS via an oxidative homocoupling and a subsequent thermal denitrogenation process. Substrates bearing a bulky or long-chain substituent gave products in good yields. This protocol is convenient and economic.2145 Ferreira et al. transformed a range of (αhydroxypropargyl)silanes to the corresponding α-silyl-β-halo enones (tetrasubstituted olefins) through treatment with NBS under mild conditions.2146 The reaction is highly stereoselective

Scheme 783

Scheme 786 Alkyl 2-deoxy-2-phenylselenyl glycosides or disaccharide derivatives were formed in high yield. The reactions are reasonably fast in acetonitrile at room temperature in the presence of 2 mol equiv of NBS and 1.5−2.0 equiv of the alcohol. The Menéndez group recently developed a fast, microwaveassisted method for the synthesis of 5,6-dihydroquinazolin-4-

and involves 1,2-silyl migration. Recently, Cai et al. carried out an effective enantioselective β-amination of chalcones with NBS into β-imido ketones using a bis(oxazoline) ligand and DBU base.2147 The method exhibits good functional group tolerance, and the products could be obtained with high enantioselectivities.

Scheme 784

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14.3. Miscellaneous Reactions Using Other Bromo-Organic Compounds

Scheme 788

Treatment of 1-methyl-5-amino- or 2-methyl-5-aminotetrazole or 3-methyl-4-amino-1,2,5-oxadiazole with dibromoisocyanuric acid afforded the corresponding azo compound in 92−98% yields.2148 DBH was applied for the synthesis of diglicodeoxynucleotides containing 2′-O-(trifluoromethyl)adenosine in the presence of HF/pyridine in dichloromethane at low temperature (Scheme 787). Using this method, the products were obtained in relatively acceptable yields under mild reaction conditions.2149 Various aromatic and heteroaromatic compounds, e.g., phenol, aniline, pyrrole, thiophene, etc., have been efficiently thiocyanated by using a combination of BDMS and ammonium thiocyanate.2150 A method for the α-thiocyanation of ketones and β-dicarbonyl compounds using the same reagent combination in acetonitrile has also been developed.2151 The developed method was mild and gave good yields of the products at room temperature. A similar transformation can also be achieved with pyridinium hydrobromide perbromide under mild and neutral conditions.2152 N,N′-Dibromo-N,N′bis[(2,5-dimethylphenyl)sulfonyl]ethylenediamine and N,Ndibromo-2,5-dimethylbenzenesulfonamide can also be used in the arene substrates in the presence of potassium thiocyanate (KSCN) to afford aryl thiocyanates (Scheme 788).2153 The reaction works best in methanol or acetic acid as the solvent. It seems likely that N-bromo sulfonamides, generated by the following reactions, are the actual thiocyanating agents involved (Scheme 789). Esters and amides were synthesized by treating the corresponding acid with a combination of equivalent amounts of triphenylphosphine and N,N-dibromo-N,N-1,2-ethanediylbis(p-toluenesulfonamide).2154 The synthesis was achieved in a two-step process. Initially, the acid was treated with PPh3 and the brominating agent. Subsequent treatment of the crude

heterocyclic, and aliphatic species. The conversion of aldoximes to nitriles could be achieved at room temperature in MeCN, Scheme 789

whereas reflux temperature was required for rapid conversion of primary amides (Scheme 791).2156 Bromodimethylsulfonium bromide was efficiently employed for chemo- and stereoselective conversions of β-dicarbonyl compounds into β-enaminones and β-enamino esters by a treatment with amines at room temperature under solvent-free conditions.2157 Das et al. carried out a condensation reaction of 1,2-diketones and 1,2-diamines for the synthesis of quinoxalines Scheme 790

Scheme 787 in an aqueous medium in the presence of tetraethylammonium bromate (Scheme 792).2158 Cyanogen bromide can be used for the synthesis of guanidines and hydroxyguanidines.2159,2160 The initial reaction was carried out by reacting CNBr with primary and secondary amines in the presence of sodium bicarbonate in ethanol at room temperature to give the respective cyanamides. The resulting cyanamides further react with amines (Scheme 793)2159 and hydroxylamine2160 to give the desired end products. CNBr is also useful for cyanation at aromatic rings. It condenses with toluene in the presence of AlCl3 to give ptoluonitrile (Scheme 794).2161 The reaction of metalated alkynides with CNBr is a useful method for the synthesis of α,β-alkynic nitriles. For example, when copper(I) phenylacetylenide was reacted with CNBr in a mixed medium of ether and acetonitrile at 35 °C, phenylpropynenitrile was produced in high yield (Scheme 795).2162 Yadav et al. have shown reactivity of alkynes with TsNBr2 toward the synthesis of α,α-dibromoalkanones and β-bromo

mixture with an alcohol or amine in pyridine at room temperature generated the corresponding ester or amide, respectively, in high yields (Scheme 790). Azetidine-2,3-diones (α-oxo-β-lactams) and bromonitromethane undergo coupling in aqueous media in the presence of a catalytic amount of sodium azide. The stereoselectivity of the process was generally good, proceeding with reasonable anti/syn ratios under substrate control. On this basis, a simple and fast protocol for the synthesis of the potentially bioactive 3substituted 3-hydroxy-β-lactam moiety was developed by Alcaide et al.2155 Bromodimethylsulfonium bromide (BDMS) was used as a useful reagent for the conversion of aldoximes and primary amides to nitriles by Yadav et al.2156 This was an operationally simple and high-yielding procedure in the absence of any base or catalyst. The optimal protocol was applicable to access a wide range of cyano compounds, including aromatic,

Scheme 791

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ethyl bromoacetoacetate in moderate yield, respectively. Cyanogen bromide serves as an equivalent of both CN− and

enol alkanoates. The method is very rapid and is carried out under metal-free conditions. When they carried out the reaction with MeCN−H2O (10:1), the α,α-dibromoalkanone products were obtained, but in the presence of carboxylic acid as the solvent, β-bromo enol alkanoates were obtained with different

Scheme 796

Scheme 792 Br+ in a cascade conversion of ketones into cyano epoxide derivatives (Scheme 799).2166 The reaction proceeds through the bromination of a ketone by cyanogen bromide, followed by

diasteroselectivities and very good regioselectivity. With arylsubstituted terminal alkynes, the E- and Z-isomers are formed via a vinylbromonium cation intermediate, while alkylsubstituted terminal alkynes provide E-selective isomers through a cyclic bromonium ion intermediate.2163 Our group has synthesized α-bromo ketones from olefins2164 at room temperature using the same brominating reagent in a binary sovent system, acetone−water (30:1). An excellent yield of the

Scheme 797

corresponding α-bromo ketone could be achieved within a short time (Scheme 796)

a nucleophilic addition of the CN− at the ketone. Subsequent intramolecular SN2 substitution of bromide by the cyanohydrin anion leads to the formation of cyano epoxide. The reaction was successfully carried out using LiHMDS as the base in DMF at room temperature. Carboxylic acids can be converted to the corresponding nitriles by treatment with CNBr at higher temperature under sealed-tube conditions. The reaction involves the intermediacy of a carboxylic cyanic anhydride. 2167 Phenol and 2,7dihydroxynaphthalene react with CNBr in the presence of

Scheme 794

Scheme 798

Scheme 793

Interestingly, with a diene system we have isolated aminobromine as a major product under similar conditions (Scheme 797). When cyclic β-dicarbonyl compounds such as barbituric acid were treated with cyanogen bromide and acetone in the

Et3N to give phenyl cyanate2168 and 2,7-dihydroxynaphthalene dicyanate,2169 respectively. Phenyl cyanate was prepared from phenol in carbon tetrachloride in the presence of triethylamine at −5 to +10 °C. Bromoamine-T can be used for the amination reaction.2170,2171 Cobalt, supported by porphyrin ligands, was capable of catalyzing intermolecular nitrene insertion of sp3 C− H bonds with bromamine-T as the nitrene source, forming the desired tosyl-protected amines with NaBr as the byproduct.2170 The reactions were carried out at room temperature in acetonitrile under a nitrogen atmosphere with bromamine-T as the reagent in the presence of 5 mol % cobalt supported by porphyrin ligands. Liu at al. have recently shown a similar C−H amination process via the formation of imido species from bromamine-T using iron as the catalyst.2171 Our group reported that a series of different substituted α-nitro ketones could be selectively cleaved and converted into the corresponding

Scheme 795

presence of triethylamine, the reaction produced the salts of triethylammonium 5-bromo-2,4,6-trioxohexahydropyrimidin-5ide and a new class of stable heterocyclic compounds, 5,5dimethyl-1H,1′H-spiro[furo[2,3-d]pyrimidine-6,5′-pyrimidine]2,2′,4,4′,6′(3H,3′H,5H)-pentaone (Scheme 798).2165 Similar compounds were obtained when the reaction was carried out using 1,3-dimethylbarbituric and thiobarbituric acid under similar conditions. The mechanistic path reveals the initial step to be a Knoevenagel condensation of the barbituric acids with acetone, followed by a Michael addition to the salt to afford the desired product. The reaction was studied with different ketones. Furthermore, the reaction of some acyclic β-dicarbonyl compounds such as diethyl malonate (DEM) and ethyl acetoacetate (EAA) with cyanogen bromide in acetone in the presence of triethylamine formed diethyl bromomalonate and

Scheme 799

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tosylamides in the presence of bromamine-T and potassium carbonate.2172 The nucleophilic Csp2−Csp3 bond cleavage of αnitro ketone in the presence of base creates new C−N bonds. A similar result for the cleavage of the C(O)−CHNO2 bond was observed when α-nitro ketone was treated with TsNBr2 under the same reaction conditions.2173 In this case, however, the corresponding tosyl amide was obtained after aqueous workup using a saturated ammonium chloride solution. We have reported a highly efficient amidation reaction of benzylic and aldehydic C−H bonds using TsNBr2.2174 In this catalyst-free protocol, the amidation of alkyl aromatics and aldehydes has been achieved using TsNBr2 via a nitrene transfer process in the presence of a base in excellent yield within a short time. The reaction was found to be selective for the secondary and tertiary benzylic C−H bonds and the C−H bond of the aldehydic group. Initially, we examined the C−H amidation reaction for alkyl aromatics (Scheme 800). The reaction was carried out by adding TsNBr2 (1 equiv) to a mixture of alkylbenzene (1 equiv) and K2CO3 (3 equiv) in ethyl acetate under an inert atmosphere at 80 °C to produce the corresponding amidated product. The reaction was extended to the nitrene insertion reaction of acyl C−H bond of aldehydes. Using the same reaction conditions, a series of aromatic and aliphatic aldehydes produced the corresponding sulfonamide in excellent yield (Scheme 801). Revesz et al. prepared four different bridged piperazine building blocks, which were 3,7,9-triazabicyclo[3.3.1]nonane, 3oxa-7,9-diazabicyclo[3.3.1]nonane, 3,6,8-triazabicyclo[3.2.2] nonane, and 3-oxa-6,8-diazabicyclo[3.2.2]nonane using N,Ndibromobenzenesulfonamide (dibromoamine-B).2175 The scaffold of 3,7,9-triazabicyclo[3.3.1]nonane was synthesized from N,N-dibromobenzenesulfonamide as the brominating agent and ethyl acrylate (Scheme 802). Alinezhad et al. have utilized NBSac as a brominating agent for the regioselective synthesis of 4-bromopyrazole derivatives from 1,3-diketones and arylhydrazines.2176 The reaction was carried out in the presence of silica gel-supported sulfuric acid as the heterogeneous catalyst under solvent-free conditions (Scheme 803). In most cases, the reaction is highly

Scheme 801

at 0−5 °C under an argon atmosphere in the dark and stirring the reaction mixture for 12 h. Ghodrati et al. have transformed thioamides to their corresponding carbonyl compounds under mild conditions using pyridinium hydrobromide perbromide as a mild and efficient reagent. The reaction was performed at room temperature using the THF/H2O solvent system.2180

15. CATALYSIS 15.1. Use of Molecular Bromine as a Catalyst

Molecular bromine can serve as a good catalyst. Thiosulfinic Sesters are readily converted to the corresponding sulfinic esters in good yields by treatment in alcohols with a catalytic amount of Br2 in the presence of H2O2. Here, sulfenyl groups are replaced by alcohols (Scheme 805).2181 The bromine-catalyzed oxidation of sulfides with hydrogen peroxide was studied by Bravo et al.2182 Dibenzyl sulfide reacts with hydrogen peroxide and a catalytic amount of bromine, leading mainly to dibenzyl sulfoxide (Scheme 806) and minor amounts of benzyl bromide, benzenemethanesulfonic acid, benzyl alcohol, and benzaldehyde. Benzyl bromide and benzenemethanesulfonic acid were obtained in almost quantitative yield by using a stoichiometric amount of bromine in the absence of hydrogen peroxide. Bjorsvik et al. reported a procedure based on Br2-catalyzed H2O2 oxidation in a two-phase system, where transformations of alkylamines to carbonyl derivatives (aldehydes, ketones, carboxylic acid, imides, lactams) through the corresponding acetamides were achieved.2183 A method for preparing alkyl pyruvate by the oxidation of alkyl lactate with H2O2 at about 25 °C in the presence of Br2 as the catalyst was presented by Lu et al.2184 Deoxygenation of sulfoxides to their corresponding sulfides can be achieved efficiently by treatment with 1,3dithiane at room temperature in the presence of catalytic amounts of bromine as the source of electrophilic bromine (Scheme 807).2185 In the synthesis of 3-amino-5-nitro-2,1-benzisothiazole and its diazonium salt, molecular bromine was used as the catalyst. 2186 A catalytic system, Br2/NaNO2/H 2O, was developed by Zhang et al. for an acid-free aerobic oxidation of sulfides. Under the optimal conditions, a broad range of sulfide substrates were converted into their corresponding sulfoxides in high yields (Scheme 808).2187 The combination of PPh3/Br2/CuBr was an effective promoter for the deoxygenation of diaryl, dibenzyl, aryl benzyl, dialkyl, and cyclic sulfoxides and gave the corresponding sulfides in excellent yield in MeCN under refluxing conditions. This reagent system is chemoselective, tolerating various functional groups such as the C−C double bond and ketone.2188 A catalytic process has been developed for aerobic alcohol oxidations in the presence of Br2 without transition metals.2189 Under the optimal reaction conditions, various alcohols were converted into their corresponding carbonyl compounds by air with a combination of TEMPO, bromine, and NaNO2 as the catalyst (Scheme 809). This catalytic system is highly efficient, especially for the oxidation of benzylic alcohols to benzaldehydes.

Scheme 800

regioselective at room temperature. However, in the case of 1,1,1-trifluoropentane- 2,4-dione, the reaction provides a mixture of regiomers at 50−60 °C. 1,2-Dibromoethane was used for the synthesis of substituted bis(2-mercaptobenzimidazole) derivatives. The reaction was carried out by heating a mixture of dibromoethane, S-1Hbenzo[d]imidazol-2-yl ethanethioate derivatives, K2CO3, and ethanol at reflux temperature. (Scheme 804).2177 A method for the synthesis of 1,2-bis(2′-xocyclohexyl)ethane has been developed by the condensation between cyclohexanone and 1,2-dibromoethane in the presence of sodium ethoxide in ethanol.2178 Tröger’s base analogues bearing methoxy groups in the 1,7-, 2,8-, 3,9-, or 4,10-positions can be converted to their dihydroxy analogues in excellent yields upon treatment with boron tribromide.2179 Reactions were carried out by adding BBr3 to the methoxy compound in DCM 6980


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Scheme 802

HBr).2191 Primary benzylic alcohols were selectively oxidized to the corresponding aromatic aldehydes by molecular oxygen in the presence of Br2−HNO3 as the catalyst in a biphasic medium of 1,2-dichloroethane and water (5:1) at 60 °C.2192 Lorkovic et al. described an integrated multistep process for the partial oxidation of alkanes to alcohols, ethers, or olefins using O2 as the oxidant. The oxidations were mediated by bromine. In the sequential transformations, first alkane was brominated to alkyl bromide and HBr. This mixture was reacted with solid metal oxide (MO) to neutralize the HBr and to generate oxygenated products or olefins and metal bromide. Oxidation of the spent solid was carried out with O2 to regenerate the metal oxide and bromine for reuse.2193 The oxidation of methylarenes to the corresponding aryl aldehydes was achieved in the presence of a

Scheme 803

Scheme 804

Scheme 805

Scheme 809

Scheme 806

mild catalytic system consisting of Br2 and DMSO under a simple operational and experimental procedure.2194 In the process for the synthesis of meptazinol, one of the substrates, hexahydro-3-(3-hydroxyphenyl)-1-methyl-2H-azepin-2-one, was prepared in 90% yield by the aromatization of hexahydro-1methyl-3-(3-oxocyclohexen-1-yl)-2H-azepin-2-one using molecular bromine at room temperature.2195 Maleic acid in aqueous H2SO4 in the presence of a relatively small amount of bromine isomerizes catalytically to fumaric acid in the dark at room temperature (Scheme 810).2196 The concomitant presence of a suitable amount of Br2 in the CCl4 phase raises the rate and yield significantly.

A similar method has been reported by Mu and co-workers for the aerobic oxidation of alcohols to the corresponding aldehydes or ketones using a catalytic system composed of Scheme 807

15.2. Catalytic Applications of NBS

NBS has been used as a catalyst for the preparation of dihydropyrimidinones (DHPMs) and the corresponding thio derivatives under microwave irradiation. By this method, a wide variety of DHPMs were synthesized in good to high yields (Scheme 811).2197 NBS efficiently catalyzes the hydroamination and hydroalkoxylation of activated styrenes using tosyl amides, carbamates, and alcohols as the nucleophiles to afford amino and ether derivatives, respectively (Scheme 812). Both the processes give good to excellent yields of the products with 100% regioselectivity (Markovnikov fashion).2198 Among the different methods reported for the synthesis of halotriazoles, the use of the NBS−CuIX (X = Br and I) system

iodoxybenzene−bromine and NaNO2.2190 The reaction was carried out using a combination of bromine (2 mol equiv) and sodium nitrite (1 molar equiv) in the presence of a catalytic amount of PhIO2 (1 mol %) in an aqueous medium. Another method was reported by Liang for the preparation of carbonyl compounds by oxidation of alcohols with oxygen or air catalyzed by tert-BuONO/Br2 (or NaNO2/HBr or t-BuONO/ Scheme 808

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was found to be the most efficient method.2199,2200 Zhang et al. used NBS along with CuI as a catalytic system in the preparation of 1,4-disubstituted 5-iodo-1,2,3-triazole through a multicomponent one-pot reaction of azides with alkynes (Scheme 813).2199 NBS has been used as an efficient catalyst for the synthesis of 14-aryl-14H-dibenzo[a,j]xanthenes under solvent-free conditions.2201 The reactions were carried out with naphthalen-2-ol and arenecarbaldehydes in the presence of NBS within 55−75 min (Scheme 814).

Scheme 812

medroxyprogesterone (MPG) was examined using NBS as the catalyst in the presence of the appropriate acid anhydride or acyl chlorides (Scheme 819).2211 The results showed that NBS could be used as an effective catalyst for the synthesis of propionate, butyrate, pentanoate, and hexanoate esters of CYP and MPG in dichloromethane at reflux temperature. NBS also serves as a good catalyst for the synthesis of polycyclic indolo[2,3-b]quinoline derivatives in good to high yields.2212 The synthesis was accomplished by mixing various arylamines, indole-3-carbaldehyde, and NBS under solvent-free conditions at room temperature (Scheme 820). Han et al.2213 described a successful catalytic Nazarov cyclization of dihydropyran substrates catalyzed by a combination of NBS and P(OPh)3 where bromonium ion was activated by the Lewis base. The reaction was effectively catalyzed by 10 mol % NBS−P(OPh)3 complex, and the products were isolated in good to excellent yields with excellent diastereocontrol (Scheme 821). Asymmetric Nazarov cyclization was also carried out by using NBS with chiral binaphthyl derivative phosphines or phosphites. An oxidative olefination reaction between aliphatic primary amines and benzylic sp3 C−H bonds has been achieved by using catalytic NBS with tert-butyl hydroperoxide as the oxidant.2214 This metal-free protocol proceeds via a direct deamination and benzylic C−H bond activation process. Heterocycles such as 2-methylquinolines and 2-methylquinoxalines were effectively converted to the corresponding olefin using this process. The primary amine in the presence of NBS and TBHP formed an imine intermediate which undergoes deimination, leading to the formation of the desired olefin (Scheme 822). Recently, Jiao et al. utilized catalytic NBS for the direct preparation of valuable α-hydroxycarbonyl compounds from carbonyl compounds. In the presence of DMSO, which acts as the oxidant, oxygen source, and solvent, a diverse range of tertiary Csp3−H bonds as well as more challenging secondary Csp3−H bonds could be hydroxylated.2215 Raju et al. have reported NBS as an efficient catalyst for the synthesis of 2-aryl/ heteroaryl-5,6-dihydro-4H-1,3-oxazines by ultrasound irradiation of 3-aminopropanol with different aryl/heteroaryl aldehydes.2216 The reactions proceeded under mild conditions and provided good yields

Scheme 810

(Acetamidobenzyl)naphthols were synthesized under mild and solvent-free conditions using NBS as a catalyst (Scheme 815).2202,2203 The reaction was carried out by treating an aldehyde, β-naphthol, and acetamide in the presence of a catalytic amount of NBS under microwave irradiation. Biologically important 1, 5-benzodiazepine derivatives were efficiently synthesized in excellent yields using catalytic amounts of NBS by Kuo et al. (Scheme 816).2204 Condensation of several aromatic as well as aliphatic ketones with substituted o-phenylenediamines was achieved in the presence of 10 mol % NBS to produce 1, 5-benzodiazepines in high yield. Yeung and co-workers presented a one-pot method for the synthesis of guanidine using NBS as the promoter.2205,2206 A number of guanidine derivatives were prepared with good to excellent yields. The reaction was carried out by treating an olefin with a nitrile, an amine, and NBS at room temperature followed by heating the resulting intermediate at 80 °C (Scheme 817). Alcohols could be oxidized to the corresponding carboxylic acid in the presence of a catalytic amount of NBS in an oxygen atmosphere.2207 The reaction was carried out with a solution of the alcohol in acetonitrile in the presence of light in an oxygen atmosphere using NBS (Scheme 818). Tong et al. have shown the catalytic efficiency of NBS for the oxidation of aromatic alcohols under aerobic conditions to the corresponding aldehyde or ketone in the presence of NaNO2 and 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ).2208 Various types of aromatic and aliphatic sulfides are selectively oxidized to the corresponding sulfoxides in high yields using 30% H2O2 in the presence of a catalytic amount of NBS.2209 The reaction was carried out by treating the sufide with 3−5 equiv of 30% H2O2 in buffered aqueous acetonitrile solution (phosphate buffer, pH 7.00) in the presence of 10 mol % NBS at 30−40 °C. Under this condition, acid-sensitive functional groups such as double bonds and O,O-acetals remain unaffected. Bandgar developed a procedure for the transesterification of β-keto esters by reaction with alcohols using NBS as the catalyst under neutral conditions.2210 Esterification of the tertiary hydroxyl group of cyproterone (CYP) and

15.3. Catalytic Use of Bromodimethylsulfonium Bromide (BDMS)

Akhlaghinia and Pourali described a method for the nitration of phenols using tetrabutylammonium nitrite in the presence of

Scheme 811

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Scheme 813

BDMS as the catalyst.2217 Nitrophenols were obtained via direct nitration of phenols with tetrabutylammonium nitrite in the presence of BDMS at room temperature in high yields under aprotic conditions. Khan et al. used this reagent as a catalyst for one-pot three-component condensation reactions of aldehydes, 2-naphthol, and thiols in acetonitrile at room temperature (Scheme 823).2218 Various aliphatic and aromatic thiols undergo conjugate addition with in situ generated enone

Scheme 814

Scheme 815

Scheme 822

Scheme 816 in acetonitrile to produce the corresponding 1-((alkylthio) phenylmethyl)naphthalen-2-ol in good yields. A one-pot multicomponent reaction of 2-aminopyridine with aromatic aldehydes and (TMS)CN under the catalytic action of BDMS was described by Venkatesham and co-workers (Scheme 824).2219 Treatment of 1 equiv each of 2-aminopyridine and (TMS)CN with 2 equiv of an aromatic aldehyde under solvent-free conditions in the presence of a catalytic amount of BDMS led to the exclusive formation of the corresponding N-benzylidene-2-phenylimidazo[1,2-a]pyridines within a short time. A method for the regioselective opening of epoxides by mercaptans to β-hydroxy sulfides and benzoxathiepinones was developed using a catalytic amount of BDMS under solventfree reaction conditions.2220 A methodology for the cyclocondensation of aldehyde, β-keto ester, and urea or thiourea in acetonitrile has been developed by using BDMS as the catalyst.2221 This process produced 3,4-dihydropyrimidin-2(1H)-ones in excellent yield. A similar method for the synthesis of 3,4-dihydropyrimidin-2-(1H)-one derivatives was also described by Bhinge et al. in the presence of a catalytic amount of BDMS.2222 Yadav et al. reported a BDMS-catalyzed

Scheme 817

Scheme 818

Scheme 819


Scheme 821

three-component coupling reaction of indoles, aldehydes, and N-alkylanilines (Scheme 825).2223 The process in ethanol as the reaction medium at room temperature could produce 3(aminoalkyl)indoles in high yields within 1.5−3.5 h. Yadav et al. reported that a combination of BDMS and ZnCl2 acts as an efficient catalytic system for the Beckmann rearrangement of various ketoximes into the corresponding 6983


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substituent hinders the formation of the dihydropyridine derivative. BDMS in combination with silver triflate provided a very efficient thiophilic promoter system, capable of activating

Scheme 824

Scheme 827

amides or lactams in MeCN at reflux temperature with good to excellent yields.2224 Later they found that BDMS alone can catalyze the Beckmann rearrangement of ketoximes in an imidazolium-based ionic liquid, [bmim]PF6, as the reaction medium (Scheme 826).2225 This modified procedure does not require any cocatalyst and proceeds with excellent conversion and selectivity. The ionic liquid was recovered and reused for up to three runs without any loss of efficiency. A convenient one-pot three-component Mannich reaction of acetophenone with aromatic aldehydes and anilines catalyzed by BDMS was described.2226 The reaction was carried out under solvent-free conditions at ambient temperature, affording the corresponding β-amino ketones in good yields. Again, 1,3dicarbonyl compounds were converted to Mannich-type products or highly functionalized piperidines in the presence of a catalytic amount of BDMS (Scheme 827).2227 The reaction was carried out with a mixture of an aldehyde, aniline, and a 1,3- dicarbonyl compound using 10 mol % BDMS in acetonitrile at room temperature.

both “disarmed” and “armed” thioglycosides for glycosidic bond formation.2231 The formation of a glycosidic bond was achieved by treating the reaction mixture with BDMS in the presence of AgOTf in dichloromethane (Scheme 829). The usefulness of this new promoter was illustrated by a successful reactivitybased one-pot oligosaccharide assembly. A one-pot three-component reaction of aldehydes, ketones, and benzyl carbamate in the presence of BDMS as the catalyst was described to afford the corresponding Cbz-protected βamino ketones.2232 β-Amino ketones were synthesized by treating equimolar amounts of aldehyde, ketone, and benzyl carbamate in the presence of a catalytic amount of BDMS in acetonitrile at room temperature (Scheme 830). The synthesis was accomplished in a short reaction time in high yields and good diastereoselectivity. A mild and rapid Michael addition of mercaptans to α,βunsaturated ketones was achieved in excellent yields using a catalytic amount of BDMS.2233 Another method for the Michael addition of a wide variety of amines to electrondeficient alkenes in the presence of BDMS as the catalyst was described by Khan and co-workers.2234Aliphatic and benzylic amines undergo conjugate addition within a very short period under solvent-free conditions at room temperature, providing excellent yields of the products (Scheme 831). The protocol was found to be chemoselective. Benzimidazoles were efficiently synthesized in high yields by the treatment of 1,2-phenylenediamine with aldehydes using BDMS at room temperature (Scheme 832).2235Aromatic aldehydes containing both electron-donating and electronwithdrawing groups could be transformed into the product in high yield. This reaction also works well for aliphatic α,βunsaturated aldehydes to provide the corresponding benzimidazole in high yield. Three-component reactions of aldehydes, amines, and allyltributylstannane were accomplished using BDMS as the catalyst. The reaction was carried out by treating aldehydes, amines, and allyltributylstannane in the presence of a catalytic amount of BDMS in acetonitrile at room temperature (Scheme 833). The reaction goes into completion within a short reaction time to afford the corresponding homoallylic amines in excellent yields.2236 A one-pot synthesis of α-amino nitriles was achieved by a three-component condensation of aldehydes, amines, and trimethylsilyl cyanide in the presence of BDMS as a catalyst (Scheme 834).2237 The products were obtained in high yields in 1−2 h of reaction at room temperature in acetonitrile as the reaction medium. Das et al. presented an efficient solvent-free synthesis of 1,5benzodiazepines2238,2239 by condensation of o-phenylenedi-

Scheme 825

The same group also presented that BDMS could catalyze Mannich-type reactions of a variety of aldimines, generated in situ from aldehydes and anilines, with enolizable ketones or diethyl malonate in three-component reactions to afford the corresponding β-amino carbonyl compounds.2228 a catalytic amount of BDMS was added to a mixture of 2 equiv of an aldehyde, 1 equiv of an aniline, and 2 equiv of a ketone in Scheme 826

ethanol at room temperature to produce the corresponding βamino carbonyl compound (Scheme 828). An aldol condensation reaction was also reported under BDMS catalysis. Yue et al. have reported a cross aldol reaction between aromatic aldehydes and ketones to synthesize α,α′bis(arylmethylidene)cycloalkanones.2229An environmentally benign one-pot synthesis of dihydropyridines and their use as a hydrogen source in the reduction of α,β-unsaturated aldehydes and ketones using a catalytic amount of BDMS at room temperature was described by Goswami et al.2230 It was observed that the presence of more than one electron-donating 6984


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Scheme 828

aldehyde, an aniline derivative, and an aliphatic isocyanide in acetonitrile in the presence of 10 mol % BDMS. High yields of the corresponding α-amino amidine derivatives were isolated at room temperature. BDMS has also been used as a catalyst for the selective photooxidation of different benzylic alcohols in the presence of

Scheme 829

Scheme 834

Scheme 830

molecular oxygen under visible light irradiation.2242 The method was found to be efficient for the oxidation of primary and secondary benzylic alcohols into their corresponding aldehydes and ketones with excellent product yield. Khan et al. have shown another catalytic protocol using BDMS for the

Scheme 831


synthesis of imidazo[1,2-a]pyridine.2243 They carried out a onepot three-component Ugi reaction by using aromatic amidine, aromatic aldehyde, and isocyanide in the presence of 5 mol % BDMS at room temperature (Scheme 838). Acetonitrile was found to be the best solvent for this process.

amines with ketones in the presence of a catalytic amount of BDMS (Scheme 835).2238 The condensation occurred at room temperature, and the products were formed in high yields. A novel solvent-free, one-pot synthesis of α-amino phosphonates in the presence of a catalytic amount of BDMS at room temperature in high yields was reported by Kudrimoti et al. (Scheme 836).2240 The method is effective for aromatic as well as α,β-unsaturated aldehydes and provides excellent yields of the product in a very short time. A wide variety of α-amino amidine derivatives were synthesized by Khan et al. via a one-pot three-component reaction from aromatic aldehydes, aromatic amines, and isocyanides in the presence of a catalytic amount of BDMS (Scheme 837).2241 The reaction was carried out by treating an

Scheme 836

Recently, Khan et al. synthesized 4-phenacylidene flavenes via a one-pot pseudo-three-component condensation reaction between salicylaldehydes and acetophenones in the presence of catalytic bromodimethylsulfonium bromide in acetonitrile at room temperature.2244 The protocol is attractive due to the simple reaction procedure, high bond-forming efficiency, and environmentally benign reaction conditions.

Scheme 833

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Scheme 837

Scheme 840

Tetrabutylammonium tribromide also serves as a suitable catalyst for the synthesis of a wide range of O-isopropylidene derivatives that can be prepared from the sugar derivatives (Scheme 843).2251 The reaction could be carried out by treating sugar with acetone at room temperature by employing just 2 mol % tetrabutylammonium tribromide to produce the corresponding O-isopropylidene derivatives in high yield. Hassan et al. found that DBH serves as an efficient catalyst for the synthesis of 2-arylbenzimidazoles by the condensation of 1,2-phenylenediamine with various aromatic aldehydes.2252 The reaction proceeds efficiently in the absence of solvent under thermal conditions and microwave irradiation in high

15.4. Use of Other Bromo-Organic Compounds as Catalysts

DBH accompanied by NaNO2 was used as a cocatalyst for the acceleration of the aerobic oxidation of benzylic alcohols in water catalyzed by TEMPO. All reactions were performed using 10 mol % TEMPO, 40 mol % DBH, and 40 mol % NaNO2 at 80 °C, and the products were obtained in good to high yields (Scheme 839).2245 DBH has also found applications as a catalyst in the oxidations of pyrazolines.2246 Conversion of various 3-arylsydnones to their corresponding 4-acetyl derivatives was achieved using DBH as the catalyst (Scheme 840).2247 The products were achieved by treating the precursor 3-arylsydnones with acetic anhydride in the presence of a catalytic amount of DBH at reflux temperature.

Scheme 841

Scheme 838 yields. They also explored the efficacy of the same catalyst for the synthesis of 1-(amidoalkyl)-2-naphthols by the condensation of 2-naphthol with various aryl aldehydes and acetamide under thermal conditions and microwave irradiation.2253 This method was also carried out under solvent-free conditions. 2Arylbenzothiazoles were efficiently synthesized in one pot from the reaction of 2-aminothiophenol and aromatic aldehydes using DBH as the catalyst.2254A similar protocol was developed under BDMS catalysis.2255 Shirini developed a methodology for Tetrabutylammonium bromide efficiently catalyzes the threecomponent coupling of a substituted aldehyde, α-naphthol or β-naphthol, and malononitrile to afford the corresponding 2aminobenzochromene. This protocol under microwave irradiation worked in the absence of an organic solvent, the yields were high, and the reactions went to completion within 2−3 min.2248 A simple, mild, and environment-friendly procedure has been developed for Knoevenagel condensation between aromatic aldehydes or ketones and malonic acid in the presence of tetrabutylammonium bromide and K2CO3 under microwave irradiation in water. The products are obtained in excellent yields and are in a state of high purity (Scheme 841).2249 While studying the solid-phase bromination of tert-butylsubstituted phenols with NBS and dioxane dibromide for the synthesis of brominated cyclohexadienones, quinobromides,

Scheme 842

the synthesis of 14-aryl-14H-dibenzo[a,j]xanthenes using DBH as the catalyst in the presence of kaolin under solvent-free conditions (Scheme 844).2256 The reaction was carried out by adding 2-naphthol to a hot mixture of aryl aldehyde, kaolin, and Scheme 843

Scheme 839

DBH at 125 °C and continuing the reaction for the appropriate time. High yields of the corresponding xanthenes were achieved within a short reaction time. DBH was also found to be an effective catalyst for the condensation of 1,2-diamines with 1,2-dicarbonyl compounds to afford the corresponding quinoxaline derivatives in excellent yields under mild reaction conditions.2257 Zhang reported that DBH can be used as an efficient catalyst in combination with tert-butyl nitrite−H2O for the aerobic oxidation of sulfides into

Voleva and co-workers found that dioxane dibromide catalyzes the anhydroheterocyclization of 2,2′-dihydroxybiphenyls.2250 They found that the treatment of 2,2′-dihydroxy-3,3′,5,5′-tetratert-butylbiphenyl with a catalytic amount of dioxane dibromide under solid-phase conditions produces 2,4,6,8-tetra-tert-butyldibenzofuran in high yield (Scheme 842). 6986


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their corresponding sulfoxides.2258 Under neutral conditions, DBH was also found to be an efficient catalyst for the acetylation of aldehydes with acetic anhydride to produce the corresponding 1,1-diacetates in excellent yields (Scheme 845).2259 Alinezhad has shown that NBSac can be used as a catalyst for the preparation of oxathiolane from aliphatic and aromatic aldehydes and ketones with 2-mercaptoethanol.2260 The reaction was carried out by treating the carbonyl compound with 2-mercaptoethanol in the presence of a 10 mol %

a solid support has also turned out to be the controlling factor for attaining selectivity. Due to the hazardous nature of Scheme 847

molecular bromine and the risk of handling it, enormous growth has been witnessed in the past several decades for the development of solid bromine carriers. This led to the introduction of a number of bromo-organic compounds for organic synthesis. However, among all such different brominating reagents, NBS has been widely used as an efficient and successful reagent for various organic transformations. The accomplishment of a high selectivity and reactivity profile in organic reactions using a particular reagent in a greener environment will remain the major challenge in the future.

Scheme 844

concentration of the catalyst in DCM as the solvent (Scheme 846). Ghorbani-Vaghei et al. recently explored the catalytic efficiency of poly(N-bromo-N-ethylbenzene-1,3-disulfonamide) (PBBS)2261 and N,N,N′,N′-tetrabromobenzene-1,3-disulfonamide (TBBDA)2262 in a multicomponent cyclization reaction. Using catalytic TBBDA/PBBS, 3-substituted indoles were synthesized from indole, aldehydes, and heterocyclic arylamines under solid-state conditions at room temperature (Scheme 847).2261 The products were isolated with good to high yield. The catalyst could be recovered from the reaction mixture for reuse. They also synthesized pyrimidine derivatives using catalytic TBBDA using a multicomponent reaction pathway.2262 The reaction was carried out by treating triethoxymethane,

AUTHOR INFORMATION Corresponding Author

*E-mail: [email protected]. Notes

The authors declare no competing financial interest. Biographies Indranirekha Saikia was born in, Jorhat, Assam, India, in 1983. In 2004, she graduated from J. B. College, Dibrugarh University, majoring in chemistry, and received her master’s degree in 2006 from the same university with specialization in organic chemistry. She obtained her Ph.D. degree in organic chemistry from Gauhati University under the supervision of Dr. Prodeep Phukan in 2012. The main focus of her work is developing new synthetic routes using bromo-organic compounds. At present, Dr. Saikia is working as a Council of Scientific and Industrial Research (CSIR) research associate at the North East Institute of Science and Technology (NEIST), Branch Laboratory, Itanagar, Naharlagun, Arunachal Pradesh, India.

Scheme 845

ammonium acetate, and ketone derivatives with a catalytic amount of TBBDA under solvent-free conditions at 100−110 °C to produce pyrimidine derivatives in excellent yield.

Arun Jyoti Borah was born in Dergaon, Assam, India, in 1983. He completed his B.Sc. (2003) degree at Dibrugarh University (D. K. D. College) and M.Sc. (2005) degree at Gauhati University, with specialization in organic chemistry. He obtained his Ph.D. degree in organic chemistry from Gauhati University under the supervision of Dr. Prodeep Phukan in 2013. Then he joined Lishui University, China, as a visiting research fellow in the group of Dr. Guobing Yan from 2014 to 2015. At present, he is working as a postdoctoral research fellow at Nanjing University, China, with Prof. Zhuangzhi Shi. His areas of research interest are asymmetric synthesis, C−H bond activation, etc.

16. CONCLUSION This review outlined different organic syntheses facilitated by bromine and bromo-organic compounds. The discussion Scheme 846

Prodeep Phukan, born in Jorhat, Assam, India, obtained his M.Sc. degree from Gauhati University, India, in 1992 and Ph.D. (under the supervision of Dr. A. Sudalai) from the National Chemical Laboratory, Pune, India, in 1999. After receiving his Ph.D., he joined Gauhati University in the same year. He carried out his postdoctoral studies at the University of Tubingen, Germany, with Prof. Martin E. Maier from January 2002 to March 2003, with a fellowship from the Alexander von Humboldt Foundation, Germany. He is also a recipient of the Ramanna Fellowship from the Department of Science and Technology (DST), India, and bronze medal from the Chemical Research Society of India. At present, he is serving the Gauhati University as a professor in chemistry. He has authored 106 peer-reviewed articles, and holds

revealed that organic transformations mediated by molecular bromine could also be facilitated by the use of other brominated compounds. Among all these, N-bromo reagents were found to be the most successful. Different reagents were found to have different reactivity profiles, and hence, the selectivity of bromination or other transformations could be controlled by choosing an appropriate bromo-organic compound. In many cases, the use of a suitable reaction medium or 6987


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(22) Rhinesmith, H. S. α,β-Dibromosuccinic Acid. Org. Synth. 1938, 18, 17. (23) Movsumzade, M. M.; Kyazimov, A. S.; Shabanov, A. L.; Alekperova, S. A. Conjugated Halogenation of Unsaturated Compounds. V. Conjugated Halogenation of Unsaturated Compounds In The Presence of Acetic Anhydride. Zh. Org. Khim. 1972, 8, 262−264. (24) Tsuchida, S.; Numata, T.; Hamanaka, S.; Ogawa, M. Bromination of 4-Vinylcyclohexene. Technol. Rep. Kansai Univ. 1972, 13, 19−24. (25) Hadjoudis, E.; Kariv, E.; Schmidt, G. M. J. Solid−Gas Reactions. Part I. Bromination. J. Chem. Soc., Perkin Trans. 2 (1972-1999) 1972, 9, 1056−1060. (26) Grinninger, L. D. Bromination of Cinnamalacetophenone. Ger. Offen. DE 2629494 A1 19770120, 1977. (27) Bottino, F. A.; Pappalardo, G. C.; Scarlata, G.; Sciotto, D.; Torre, M. Nitration and Bromination of l, 1-diphenyl-2-(2-thienyl) ethylene. Can. J. Chem. 1978, 56, 2755−2757. (28) Naae, D. G. Electrophilic Bromination of Fluoro Olefins: Syn Vs. Anti Addition. J. Org. Chem. 1980, 45, 1394−1401. (29) Harwood, L. M.; Julia, M.; Le Thuillier, G. Organic Synthesis With SulphonesXVII1: The Anti-Markownikoff Halosulphonylation of Olefins via an Ionic Pathway, and A New Method of Preparing Benzenesulphonyl Iodide. Tetrahedron 1980, 36, 2483−2487. (30) Friedman, L.; Callaway, C. 1, 2-Dibromo-3-chloropropane (DBCP). U.S. US 4385192 A 19830524, 1983. (31) Moon, D. W. The Radical Bromination Reaction of Ethylenecarbonate. Arch. Pharmacal Res. 1983, 6, 1−6. (32) Salakhov, M. S.; Nagiev, V. A. Synthesis of Highly Halogenated Imides of Cyclic 1,2-Dicarboxylic Acids. Monomery Polim. 1983, 3−7. (33) Mayr, H.; Will, E.; Heigl, U. W.; Schade, C. Bromination of Octmethylcyclopentene - The Irregular Reactivity of A Sterically Hindered Cycloalkene. Tetrahedron 1986, 42, 2519−2522. (34) Zabicky, J.; Nutkovitch, M. Reactions of Bromine and Cyclohexene in Aqueous Media. Selectivity of Bromohydrin vs. Dibromo Adduct Formation. Ind. Eng. Chem. Prod. Res. Dev. 1986, 25, 372−375. (35) Aliev, F. Ch.; Shabanov, A. L. Joint Bromination of Chloroprene and Oxirane. Azerb. Khim. Zh. 1986, 5, 45−48. (36) Fetyukhin, V. N.; Kobrzhitskii, V. V.; Samarai, L. I. Bromination of 2, 4- and 2,6-Tolylene Diisocyanates. Zh. Org. Khim. 1987, 23, 2161−2170. (37) Taniuchi, A.; Nakano, T.; Nishibori, S. Preparation of Hexabromocyclododecane. Eur. Pat. Appl. EP 276859 A1 19880803, 1988. (38) Shi, X.; Day, R.; Miller, B. Bromine-Induced Aromatic Alkylation and Dienone-Phenol Rearrangements. J. Chem. Soc., Perkin Trans. 1 1989, 6, 1166−1167. (39) Arcus, C. L.; Strauss, H. E. The Addition of Bromine To (+)-1Phenylallyl Alcohol and The Oxidation of The (+)-Dibromo-Alcohol. J. Chem. Soc. 1952, 2669−2671. (40) Chou, S. S. P.; Kuo, H. L.; Wang, C. J.; Tsai, C. Y.; Sun, C. M. Regiospecific and Stereospecific Synthesis of E- and Z-Trisubstituted Alkenes via 2,2-Disubstituted Vinylsilanes. J. Org. Chem. 1989, 54, 868−872. (41) Font, J.; Gracia, A.; De March, P. Reaction of Methyl 2, 3Pentadienoate with Bromine. Preparation of 4-Bromo-5-Methyl-5HFuran-2-One. Tetrahedron 1990, 46, 4407−4416. (42) Lukovskaya, E. V.; Bobyleva, A. A.; Pehk, T.; Belikova, N. A. Reaction of Cis-Bicyclo[4.3.0]Nonadienes with Bromine and Mixed Halogens. Zh. Org. Khim. 1991, 27, 345−354. (43) Fuller, C. E.; Walker, D. G. An Improved Synthesis of Isomerically Pure Cis- 1-Bromopropene. J. Org. Chem. 1991, 56, 4066−4067. (44) Bellucci, G.; Bianchini, R.; Chiappe, C. Bromination of Alkenes in Acetonitrile. A Rate and Product Study. J. Org. Chem. 1991, 56, 3067−3073. (45) Zelikman, V. M.; Mendeleeva, E. A.; Smirnov, V. V.; Zyk, N. V.; Shilina, M. I.; Zefirov, N. S. Bromochlorination of Unsaturated

three Indian patents. His current area of research focuses on asymmetric synthesis, catalysis, computational organic chemistry, and development of new synthetic methods.

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