Sulfamic Acid and Its N- and O-Substituted Derivatives - Chemical

Review pubs.acs.org/CR

Sulfamic Acid and Its N- and O‑Substituted Derivatives William Spillane* School of Chemistry, National University of Ireland, Galway, University Road, Galway, Ireland

Jean-Baptiste Malaubier Manufacturing Science and Technology, Roche Ireland Limited, Clarecastle, Co. Clare, Ireland 2.14.2. NH2SO2Cl and N-Monosubstituted Halides 2.14.3. N,N-Dimethylsulfamoyl Halides 2.14.4. Sulfamoyl Fluorides 2.14.5. Sulfamoyl Azides 3. Noncyclic Sulfamate Esters 3.1. Structural Studies 3.2. Synthesis 3.2.1. Use of R3N−SO3, NH2SO3H, and SO3 3.2.2. Miscellaneous 3.3. Reactions 3.3.1. Amination and Amidation 3.3.2. Aziridination 3.3.3. Other Reactions 3.4. Mechanistic Studies 3.5. N-Acylsulfamates 3.6. N-Sulfonate Carbamates 4. Cyclic Sulfamate Esters 4.1. Structural Studies 4.2. Synthesis 4.3. Reactions 4.3.1. Nucleophilic 4.3.2. Other Reactions 4.3.3. Mechanistic Studies 5. Esters Biological Studies 5.1. Carbonic Anhydrase (CA) Inhibition 5.1.1. Reviews 5.1.2. X-ray and Computational Studies 5.1.3. Inhibitors 5.1.4. Topiramate and Related Compounds 5.1.5. Other Medicinal Uses 5.2. Steroidal Sulfatase Inhibitors (SSIs) 5.2.1. Reviews 5.2.2. Introduction 5.2.3. Substitution in the A Ring at the 2 and 3 Positions 5.2.4. Substitution in the D Ring at the 17 and Other Positions 5.2.5. Major Changes in the A and D Rings 5.2.6. Bis-Sulfamates 5.3. Nonsteroidal Sulfatase Inhibitors (NSSIs) 5.3.1. Reviews 5.3.2. Phenyl and Biphenyl Compounds

CONTENTS 1. Introduction 2. Sulfamic Acid 2.1. Computational Studies 2.2. Structural Studies 2.3. Magnetic and Spectroscopic Studies 2.4. Ionization and Kinetic Studies 2.5. Solubility, Conductance, and Miscellaneous Studies 2.6. Synthesis 2.6.1. Sulfamic Acid and Aliphatic and Alicyclic Sulfamates 2.6.2. Aryl- and Heterosulfamates 2.6.3. Other Sulfamates 2.7. Reactions 2.8. Sulfamate−Metal Bonds 2.9. Analytical Aspects 2.10. Industrial Aspects 2.11. Sulfamic Acid and Sulfamates as Catalysts 2.11.1. Esters 2.11.2. Ethers, Acetals, Ketals, and Anhydrides 2.11.3. Aldehydes and Ketones 2.11.4. Amides, α-Aminonitriles, and Amines 2.11.5. N-Heterocycles 2.11.6. O-Heterocycles 2.11.7. O−N and S−N Heterocycles 2.11.8. Polymers and Miscellaneous Reactions 2.12. Amine Sulfur Trioxide Adducts: R3N−SO3 2.12.1. Computational and X-ray Studies 2.12.2. N-Sulfonation 2.12.3. O-Sulfonation 2.12.4. C-Sulfonation and Miscellaneous Reactions 2.13. N-Sulfonylamines 2.14. Sulfamoyl Halides and Azides 2.14.1. Physical Studies

© XXXX American Chemical Society

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Received: April 29, 2013

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Chemical Reviews 5.3.3. Benzoic and Cinnamic Acids and Ketones 5.3.4. Heterocycles 5.3.5. Tyramine Derivatives 5.3.6. Tricyclic Coumarin Sulfamates 5.3.7. Dual Aromatase−Steroidal Sulfatase (DASI) 5.4. Other Medicinally Important Esters 5.4.1. Carbohydrate, Amino Acid, and Peptide Sulfamates 5.4.2. Nucleoside and Nucleotide Sulfamates 5.4.3. Inhibitors, Agonists, Natural Products, Etc 6. Sulfamides 6.1. X-ray Studies 6.2. Computational, Spectroscopic, and Magnetic Studies 6.3. Inorganic, Industrial, and Analytical Studies 7. Alicyclic Sulfamides 7.1. Synthesis 7.1.1. Mono- and Disubstituted 7.1.2. Tri- and Tetrasubstituted 7.1.3. Metal Catalyzed 7.1.4. Use of Boc and Other Reagents 7.2. Reactions 7.2.1. Metal Catalyzed 7.2.2. Other Reactions 7.2.3. Mechanistic Studies 7.3. Biological, Medicinal, Inhibition, and Other Uses 7.3.1. CA and Kinase Inhibitors 7.3.2. Protease Inhibitors 7.3.3. Inhibition of Other Enzymes 7.3.4. Protein Inhibitors 7.3.5. Agonists and Antagonists 7.3.6. Benzo-Fused Heterocycles 7.3.7. Other Uses 7.4. Agrochemical and Applied Uses 7.4.1. Agrochemical 7.4.2. Applied 7.5. N-Acylsulfamides 7.5.1. Synthesis 7.5.2. Reactions 8. Cyclic Sulfamides 8.1. X-ray and Computational Studies 8.2. Synthesis 8.2.1. Reviews 8.2.2. Four-, Five-, Six-, and n-Membered Rings 8.2.3. Multiring Heterocycles 8.2.4. Macrocyclic Heterocycles 8.2.5. Sulfahydantoins: Five- and Six-Membered Rings 8.3. Reactions 8.3.1. Metal-Catalyzed and Chiral Auxiliaries 8.3.2. Five-Membered Rings (Thiadiazole 1,1Dioxides) 8.3.3. Six-Membered Rings (Thiadiazine 1,1Dioxides) 8.3.4. Seven-Membered Rings, Bicycles, and Multiring Heterocycles 8.4. Biological, Medicinal, Inhibition, and Other Uses 8.4.1. Reviews

Review

8.4.2. CA and Protease Inhibitors 8.4.3. γ-Secretase and Other Enzyme Inhibitors 8.4.4. Agonists and Other Uses Author Information Corresponding Author Notes Biographies Acknowledgments Abbreviations References

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1. INTRODUCTION In 1980 sulfamic acid and its N-substituted derivatives were reviewed in Chemical Reviews,1 effectively updating an earlier 1940 review2 also in Chemical Reviews. In 1991 the subject was again comprehensively reviewed,3 and since a further 20 years have passed it was felt that there was a need for a new review that could bring together the many and diverse areas of sulfamic acid chemistry and especially the whole area of sulfamate esters, RNHSO2OR, which has emerged in the last 18 or so years as being of immense importance in biological and medicinal chemistry. This task rather unexpectedly received new immediacy and urgency when it was reported recently that the 1980 Chemical Reviews article for a time topped the ACS list as “the most read” Chemical Reviews in 2011 on a list containing in the main articles that had appeared over the past few years. There has thus been a massive surge in interest in various areas of sulfamic acid chemistry, most particularly in use of the acid and certain derivatives as catalysts in organic chemistry and synthesis of esters and their demonstrated use and potential in many areas of medicinal chemistry. As in our previous reviews in 1980 and 1991 certain areas which might be seen as being peripheral to sulfamic acid chemistry have been excluded. This policy was adopted again in the present review in order to avoid a review of inordinate length. Thus, for example, the whole area of sulfonamides, RNHSO2R, chlorosulfonyl isocyanates (CSIs), heparin, and monobactams has not been covered. Use of the Burgess reagent is covered where it has been employed to synthesize sulfamates. These areas have all been reviewed more than once in recent years. There have been a number of short reviews pertinent to this work that have appeared over the last 15 years or so, and these have highlighted various aspects of sulfamic acid and sulfamide chemistry. An important encyclopedia on reagents for organic synthesis4,5 has useful entries on both as has a compendium on organic functional group transformations.6 A 2007 chemical technology encyclopedia has a substantial number of short entries on sulfamic acid, sulfamates, sulfamoyl halides, sulfonation, sulfation, and sulfur compounds.7 In the present review we covered the 21 year period from 1991 to the end of 2011. Papers published prior to 1991 are generally not referenced in the current review unless they were inadvertently omitted in the two earlier reviews or unless their inclusion now is deemed necessary for a fuller understanding of the work being reviewed.

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2. SULFAMIC ACID

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2.1. Computational Studies

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Several ab initio SCF(self-consistent field)-MO studies of sulfamic acid,8−10 sulfamate anion,10 NH2SO3−, and Nmethylsulfamate anion,8 MeNHSO3−, have been reported.

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potassium salt, MeNHSO 3 K, 36 of N-[1-(acetylamino)ethylidene]sulfamic acid, MeCONHC(Me)NHSO3H,37 of

Calculations using the 6-31G** basis set gave an N−S bond length for zwitterionic sulfamic acid of 1.95 Å compared to a solid-state value of 1.76 Å.9 The nonzwitterionic form of sulfamic acid was predicted to be more stable by 0.01 Eh (hartree unit) per molecule in the gas phase than the zwitterionic form.10 Studies at the 6-31G** level on sulfamic acid and its complexes with NH3, H2O, and HF have also been reported.11 Sulfamic acid and sulfamide have been included with a series of over 10 biologically active sulfonamides (and their anions) in theoretical quantum chemical calculations on the study of their stable geometries and gas-phase acidities. For sulfamic acid and sulfamide the calculated acidities correlate well with the experimentally determined pKa values.12 Further SCF-MO calculations on the sulfamate anions, RNHSO3− (R = Me,13,14 Et,13,14 and iPr13), have been reported.

the cyclamates38 cyc-C6H11NHSO3M, M = H, Na, K, NH4+, Rb, and (nPr)4N+, and of acesulfam-K,39 4, have been reported. Another cyclic sulfamate related to acesulfame, 6-chloro-4phenyl-1,2,3-benzoxathiazine 2,2-dioxide, 5, has had its X-ray crystal structure reported.40

2.2. Structural Studies

The microwave spectrum of zwitterionic sulfamic acid has the expected C3v geometry with an N−S bond length of 1.957 Å.15 The dative bond between nitrogen and sulfur is believed to be only partially formed. The 14N−1H dipolar tensors of sulfamic acid have been determined from a solid-state NMR single-crystal study.16 X-ray crystal structures have been determined for lithium,17 rubidium,18 and cesium19−21 sulfamates. Structures have also been reported for the double salts MLi(NH2SO3)2, where M = K, Rb, and Cs,22 CsNHSO3H·NH2SO3H,23 and (NH4)2SO4·NH2SO3H.24 Structures of Me2NCHN+HSO3− generated from reaction of DMF and the putative N-sulfonylamine, NHSO2 (see section 2.13), has been reported25 and of the 1:1 complex between benzo-18-crown-6 and sulfamic acid.26 Structures of the copper π-complexes [Cu(NH2SO3) 2]· (C 3 H 8 N)(H 2 O) 27 and [(CH 2 CHCH 2 ) 2 N−CHO](Cu(NH2SO3)2(H2O)28 and the 4-allylthiosemicarbazide complex [Cu(CH2CHCH2NHNHCSNH2)]NH2SO329 have been de-

Several other heterocyclic sulfamate structures have been determined.41−43 The 6-amino-2,4-dioxo 1,2,3,4-tetrahydropyrimidine-5-sulfamic acid, 6,42 (7-amino-2,3-dihydro-5-oxo-5Hthiazolo[3,2-a]pyrimidin-6-yl)sulfamate, 7,42,43and the related (8-amino-3,4-dihydro-2H,6H-pyrimido[2,1-b][1,3]-thiazin-6on-7-yl)sulfamic acid.42 Structures of two bis-sulfamates have been published.44,45 Ethylenediamine bis-sulfamate,44 H3N+SO3−NH2(CH2)2NH2−O3SNH3+, and a 2:1 bis(betaine) sulfamate45 in which monoprotonated betaine dimers (Me3NCH2CO2)H+ and sulfamate anions are involved. In order to calculate structure/structure and structure/ reactivity correlations for sulfamates and sulfate monoesters crystal structures were determined by low-temperature X-ray crystallography for the following 11 sulfamate esters (NH2SO2O−Ar (or R), Ar = XYC6H4; X, Y = p-NO2, H; pMeO, H; m-NO2, H; m-Cl, H; p-Cl, H; p-CN, H; H, H; p-I, H; m, p-NO2; R = Et, 2,2,2-F3CCH2) and also for several sulfates.46 The X-ray crystallographic structure of 5-deoxy-5-iodo-2,3-O(1-methylidene)-4-methylthiocarbonyl)-α-L-sorbopyranose sulfamate 8 has allowed the relative and absolute stereochemistry to be established.47 Compound 8 possesses potent anticonvulsant activity. The conformational preferences for a series of 2,3-Oisopropylidene-α-L-sorbopyranose derivatives were determined from proton NMR data and empirical forced field calculations.47 A twist−boat or skew conformation is favored over a chair form. Crystal structures have been reported for the mono- and difluorosulfamate anions F−NHSO3 and F2−NSO3, respectively.48 A report on growing single-crystal sulfamic acid from aqueous solution by the Sanakaranarayanan−Ramasamy method has been reported.49 X-ray powder diffraction, Raman, FTIR, and optical transmission studies were performed.

termined. A crystal structure has been reported for p-nitrobenzoxasulfamate monohydrate 1, and differential thermal analysis (DTA) and thermal gravimetric (TG) studies are also given,30 and an X-ray structure of the first metal complex of 1, namely, triaquabis(p-nitrobenzoxasulfamato)copper(II) monohydrate, has been determined by the same group.31 Crystals structures for the calcium and nickel tetrahydrates M(NH2SO3)2·4H2O have been determined.32 Reaction of silver oxide with sulfamic acid in a 30% ammonia and 4% NaOH environment led to formation of the polymer [NaAg-

(NH2SO3)2]n in which X-ray crystal analysis shows a 3dimensional framework with Na−O bonds.33 Crystal structure analysis has been made on the 3-carboxypyridinium ammonium sulfate sulfamic acid complex 2,34 while the L-histidinium monosulfamate 3 has been the subject of an IR and Raman comparative study.35 Structures of a number of organic sulfamates have been determined including a series of cyclamate and acesulfame sweeteners. Structures of N-methylsulfamic acid and its

2.3. Magnetic and Spectroscopic Studies 14

N, 15N, and 17O NMR were used to study reactions of sulfamic acid with nitrite complexes of palladium, ruthenium, and rhodium giving cis-nitroaqua complexes.50 Development of the correct experimental conditions has very recently allowed detection of 1H and 15N NMR resonances in aqueous solution in heparin sulfate by slowing down solvent exchange of the sulfamate protons so that they can be observed.51 An ESR study C


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the mechanism of hydrolysis and argue against a transition state (TS) containing a zwitterion63 favoring instead association of Scheme 1. Hydrolysis of Ammonium Nitridotrisulfonate, Ammonium Imidodisulfonate, and Ammonium Sulfamate

of Cu2+-doped barium sulfamate single crystals where the paramagnetic copper ion was introduced during growth of the crystals has been reported.52 The preparation, crystal structure and magnetic properties of a new TEMPO·sulfamate salt 9, as its tetraphenylphosphonium salt have been reported as has the tetrathiafulvene salt.53 Using pulsed nozzle FT microwave spectroscopy NH3+SO3− has been observed in the gas phase. An N−S bond length of 1.957(23) Å and an NSO angle of 97.4(4)° have been reported, and the N−S dative bond is thought to be only partially formed.15 IR spectra have been reported on a series of sulfamate salts of potassium, barium, lead, cadmium, and magnesium, and the absorption bands observed have been assigned.54 Further work using IR, Raman, and 13C NMR on the 2:1 bis(betaine) sulfamate (see section 2.245) has been reported.55 An EI/MS study of seven bis-O-(1-methylethylene)fructopyranose sulfamates including the well-known anticonvulsant topiramate 10 have revealed the fragmentation patterns, and the mechanisms involved are discussed.56

sulfamic acid molecules with water in the TS. The kinetics of hydrolysis of ammonium nitridotrisulfonate, ammonium imidodisulfonate, and ammonium sulfamate in aqueous acid solutions all producing ammonium sulfate have been examined (Scheme 1). Rate laws have been derived for each compound, and in each case there is a dependence on acid and substrate.64 A kinetic study of the reaction of nitrous acid with sulfamic acid and urea has been reported, and kinetic equations have been derived.65 2.5. Solubility, Conductance, and Miscellaneous Studies

Several papers deal with the solubility of sulfamates in water. The kinetics of the dissolution and crystallization of sulfamic acid in water have been extensively probed.66 The same group performed a detailed study of the solubility in water of sulfamic acid at temperatures from −6.2 to 103.2 °C, and phase diagrams are presented showing characteristic points in the sulfamic acid− water system.67 They also looked at the thermodynamic aspects (free energies and enthalpies of dissolution and entropies) of the solubility of sulfamic acid and a large number of mono-, di-, and trivalent salts of sulfamates.68 There are also useful tables of solubilities (g/100g water) included. The solubility of lithium sulfamate in water has been examined from −42.7 to 0 °C.69 In a study of solvent effects on zwitterionic sulfamic acid the results of the effect of medium on the energy, structure, charge distribution, and vibrational frequency have been reported.70 The calculated covalent bond order for the N−S bond is 0.46, which is much larger than that calculated for the B−N bond in BH3·NH3. Impedance spectroscopy has been employed to study the electric properties of potassium sulfamate single crystals.71 The conductance of dilute solutions of sulfamic acid at 25 °C has been measured in aqueous MeOH, aqueous EtOH, and aqueous iPrOH, and limiting conductances (Λ0) and association constants (Ka) have been measured. Measurements were made in pure water and from 20% to 90% (w/w) aqueous alcohol mixtures.72 pKa values of sulfamic acid determined by pH potentiometry and conductometry are in excellent agreement, but for four haloacetic acids they are widely divergent.73 A hitherto unknown nitrogen−sulfur compound, diimide Ssulfonate, H2NNSSO3 ⇌ HNNSSO3H, may have formed on electrolysis of sodium sulfamate. UV, IR, and MS studies support its formation, and a mechanism involving the slow formation of hydrazinedisulfonate, (O3SNHNHSO3)2−, has been proposed.74 Dithionate ions, [O3S−SO3]2−, were detected in the anodic decomposition products of sulfamate solutions using differential pulse polarography (DPP), IR and Raman spectroscopy, stress measurements, and chemical analysis.75 Partial molar volumes have been determined for zwitterionic sulfamic acid, neutral sulfamic acid, and protonated sulfamate

2.4. Ionization and Kinetic Studies

The standard enthalpy of ionization of sulfamic acid in aqueous solution has been measured as 735 ± 200 J·mol−1 at 25 °C, and the standard enthalpy of solution of crystalline sulfamic acid also at 25 °C is 19.2 ± 0.2 kJ·mol−1.57 pKa values for the ionization of sulfamic acid and N-methyl- and N-ethylsulfamic acids in water, methanol, and DMF and IR data for the zwitterions and anions are reported.58 The same group has shown that protonation of Nmethyl- and N-ethylsulfamic acids is governed by the amide acidity function (HA) and most probably takes place on nitrogen RNHSO3H + H+ ⇌ RN+H 2SO3H

Their study operated over a 17.3−92.0% sulfuric acid range, and the chemical shifts on increasing protonation were probed used 1H and 15N NMR.59 The acidities of a series of seven cyclic sulfamates 11 have been determined in 60% (v/v) aqueous EtOH by potentiometric titration, and the pKas vary from 4.62 for 11 when X = Y = H to 2.33 11 when X = H, Y = 6-NO2, and a Hammett plot of the data gave a Hammett ρ value of 2.74.60 Raman spectra suggest that protonation of hydroxysulfamic acid in aqueous perchloric acid takes place on nitrogen giving HONH2+SO3− rather than on oxygen giving the neutral form HONHSO3H. A pKa of ∼−0.18 has been found.61 The kinetics of the esterification of sulfamic acid were found62 to be first order in acid and zero order in alcohol (R = Me and nC16H33). NH 2SO3H + ROH → NH 2SO2 OR

The kinetics and mechanism of hydrolysis at 80−120 °C of sulfamic acid at pHs 1.5, 4.1, and 5.7 and the activation energy Emax (142 kJ/mol) and entropy (ΔS0 = 20 ± 2 J/mol·K) have been determined. The authors disagree with earlier research on D


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ions in solution.76 Elastic (cij) and thermoelastic constants have been measured for sulfamic acid and a series of sulfamates from

sweeteners has been reviewed,86,87 and one of these reviews87 also deals with the sweetener saccharin 14 which is regarded as a

sulfa sweetener. The structure−taste aspects of sulfamate sweeteners have also been reviewed.88 Another cyclic sulfamate sweetener, acesulfame-K 4, has also been reviewed relatively recently.89 Details on the synthesis of acesulfame nontoxic salts using sulfamic acid and diketene followed by cyclization with sulfur trioxide have been published.90 Phosphonium acesulfame salts (C6H13)3P+R (R = Et, nPr, nBu, n-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, and ncapryl) 15 have been proposed as new “green” alternatives to volatile organic solvents in a variety of applications.91 An unusual synthesis of 4 has been reported using phenols and SO2Cl2 in the presence of a quaternary ammonium catalyst and diketene with an amine catalyst.92 Two older reviews of acesulfame are useful for synthesis and chemical properties, stability, sensory properties, toxicology, analytical methods, and structure−taste relationships.93,94 Unterhalt prepared 11 alicyclic sulfamates with ring sizes from 4- to 8-membered containing one or two sulfur atoms in place of carbon, and some of these have reasonable sweetness.95 The

ultrasonic resonance frequencies of thick plates.77 The liquid eutectic mixture N-methylurea-sulfamic acid has been studied in the temperature range 291.7−313.2 K using ultrasonic shear waves in the frequency range 12−80 MHz.78 Reaction of the cobalt complex Co(OCOMe)2 with 2,2′-bipyridine and sodium sulfamate gave the di-12 and mono-13 nuclear Co complexes.79 2.6. Synthesis

2.6.1. Sulfamic Acid and Aliphatic and Alicyclic Sulfamates. Synthesis of sulfamic acid from reaction of urea with fuming H2SO4·nSO3 at 55−60 °C over 4.5−7 h gave a yield of 85−90%.80 Another manufacturing process also uses H2SO4 and urea in the presence of sulfur trioxide at 70 °C giving 60% product.81 A liquid−liquid homogeneous phase method for manufacture of sulfamic acid again from fuming H2SO4 and urea is superior to conventional methods since reaction temperature can be controlled more efficiently.82 The urea, H2SO4, and SO3 process for continuous manufacture of sulfamic acid has been improved using a mechanical device which lowers the free SO3 content and increases the yield of sulfamic acid.83 A new route to sulfamic acid salts uses thioacetamide in water at 0 °C with sulfur dioxide bubbled through the reactor giving a 65% yield of product. It would be interesting to know if this reaction can be applied to other thioamides as this could then provide a useful alternative route to simple sulfamic acid salts, but the authors have not explored this.84

effect of stereochemistry on taste has been examined for some of these analogs of cyclamate, and it was found that cis-16 and trans17 show sweetness but trans-16 and cis-17 show no sweetness.96 The S-(−)-3-thiacyclopentylsulfamate 18 was twice as sweet as its racemate, but with S-(−)-3-thiacyclohexylsulfamate 19 the racemate was sweeter.97 4-Methyl-3-thiacyclopentylsulfamate is sweet, but the compounds with the methyl group in the 2 and 5 positions are not sweet. The corresponding oxa analogs (oxygen replacing sulfur) are not sweet.98 A series of 24 disulfamates, RN(SO3Na)2, and a few tri- and tetrasulfamates have been reported.99 2.6.2. Aryl- and Heterosulfamates. Interest in the structure−taste relationships of various mono- and disubstituted phenylsulfamates increased after the discovery in 1989 of the sweetness of some meta-substituted phenylsulfamates.100 Seventy five meta-, ortho-, and para-substituted phenylsulfamates were synthesized, and structure−taste relationships using linear and quadratic discriminant analysis (LDA and QDA) and classification and regression tree analysis (CART) were derived.101−103 Fourteen compounds were misclassified in the CART analysis. Seventy disubstituted phenylsulfamates were also synthesized and structure−taste relationships found using CART analysis, which misclassified only eight compounds.104,105

MeC(S)NH 2 + SO2 + H 2O → NH 2SO3−MeNH3+·H 2O + S

A versatile process for synthesis of tetrabutylammonium salts of acylsulfamates CONHSO3− involves reaction of carboxylic acids with tetrabutylammonium sulfamate with di-tert-butyldicarbonate in pyridine solvents at 20 °C giving very high yields.85 The method works well for a number of carboxylic acids including aromatic and heterocyclic substrates. RCO2 H + NH 2SO3−Bu4N+ → RCONHSO3−Bu4N+

Much interest has focused on alicyclic sulfamate synthesis because the best known one cyclamate, cyc-C6H11NHSO3−, is known for many years to be a sweetener. The topic of cyclamate E


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2.6.3. Other Sulfamates. The nimesulide prodrug sodium (N-methylsulfonyl)-N-(4-nitro-2-phenoxyphenyl)sulfamate 22 has potential as an anti-inflammatory and analgesic agent because of its wettability, solubility, and stability.112 Three novel 2-alkylpyrrole sulfamates, e.g., 23, have been isolated from the marine worm Cirriformia tentaculata.113 Four new indoles, e.g., 24, containing at least one sulfamate group have been isolated from the New Zealand sponge Ancorina sp. whose extract showed HIV-inhibitory activity.114 The hydrophobic polyelectrolyte polysodium (sulfamate− carboxylate)isoprene (SCPI) 25 complexation with hen egg lysozyme at pH 7 and 3 has been studied.115 Synthesis of SCPI-b2-vinyl pyridine was carried out by anionic polymerization highvacuum techniques and postpolymerization functionalization reactions.116 The nanostructures formed in mixed solutions of a double hydrophilic anionic−neutral block copolymer poly[(2sulfamate-3-carboxylate)isoprene-b-ethylene oxide (SCIEO) and the surfactant Me2N+(n-C12H25)2·Br− have been investigated.117

Series of N-benzaldehyde 20 (R = H), N-acetophenone 20 (R = Me), and N-benzophenone 20 (R = Ph) iminylsulfamates and N-i-butyrophenone 20 (R = iPr) iminylsulfamate were prepared from the parent hydrazones, but these compounds disappointed from the perspective of sweetness since their taste portfolios only indicated small elements of sweetness present in some of them.106 The chalcone sulfamate 21 was more than 350 times sweeter than sucrose on a weight basis.107 Thirty two heterosulfamates have been synthesized and had their taste portfolios determined, and they have been combined with 69 other heterosulfamates for which taste data are available in order to derive structure−taste relationships for this class of sulfamate. This set of 101 heterosulfamates (both cyclic and open chain) have been examined using LDA and QDA and CART analysis with some success. The CART method correctly classified 86% into sweet (S) and nonsweet (N) categories.108 Through further synthesis an enlarged set of 132 sulfamate salts was assembled, and CART analysis correctly classified 81% of this larger set.109 In a subset of 58 five-membered aromatic ring heterocycles containing thiazoles, benzothiazoles, and thiadiazoles for which taste data was obtained CART analysis classified 46 compounds from a training set of 47, and 7 of the 10 compounds in a test set were correctly classified.110 The effect on sulfamate taste of introduction of heteroatoms in place of carbon(s) was examined using 70 heterosulfamates and their corresponding carbon analogs. On substitution no change in taste occurred in 33 cases,

Scheme 2. Sulfonation of 4-R-2-Aminothiazoles and Subsequent Rearrangement

2.7. Reactions

Sulfonation of 4-R-2-aminothiazoles [R = Me, p-BrC6H4− (or pCl or m-NO2)] with chlorosulfonic acid gave mainly the Csulfonated product 2-amino-5-thiazolylsulfonic acids which can then interestingly undergo thermal isomerization into the corresponding 2-thiazolesulfamic acids in Scheme 2.118 Many years ago Hurd and Kharasch119 found that 4-methyl-2thiazolesulfamic acid undergoes the reverse reaction, isomerizing to 2-amino-4-methyl-5-thiazolesulfonic acid. Sulfonation of some substituted anilines under microwave, solvent-free conditions gave 74−93% yields of sulfonic acid products. A mechanism involving the classic aniline sulfonation pathway including phenylsulfamic acid has been suggested.120 Photolysis at 254 nm in degassed MeOH solutions of some parasubstituted sodium phenylsulfamates leads to some photo-Fries rearrangement and photodegradation to anilines. However, the three halogenosulfamates studied did not rearrange but degraded to anilines and photosolvolyzed to p-methoxyphenylsulfamate.121 Some years ago a Russian group carried out important studies on reactions of sodium, potassium, and ammonium alkylsulfamate salts with epoxides. They showed that these sulfamic acids

sweetness was lost in 29 cases, and in 8 cases sweetness was induced.111

Scheme 3. Reaction of Metal Alkylsulfamates and Epoxides Giving Hydroxysulfamates

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reacting with epoxides gave hydroxysulfamates in 50−95% yields following the reaction shown in Scheme 3.122 More than 10 products could be made by variation of R and R1 in the starting materials. A Japanese patent describes the synthesis of sodium N,Nbis(hydroxyethyl)sulfamate, (HOCH2CH2)2NSO3Na, in 96% yield by reaction of sodium sulfamate, ethylene oxide, and KOH in xylene at 130 °C for 10 h, whereas an alternative route involving sulfamation with pyridine−sulfur trioxide of (HOCH2CH2)NH gave a 40% yield.123 The Russian group extended their work on the synthesis of βhydroxyalkylsulfamates by examining reactions of sulfamic acid and N-alkylsulfamic acids with glycidol, epichlorohydrin, and epoxy ethers124 and diglycidyl and allylglycidyl ethers.125 Hydroxypropylsulfamates have been shown to undergo further reactions. Thus, 3-chloro-2-hydroxypropylsulfamate, RN(SO3M)CH2CH(OH)CH2Cl, hydrolyzes in basic conditions to 2,3-dihydroxypropylsulfamate, RN(SO3M)CH2CH(OH)CH2OH,126 and reacts with amines to give 1,3-diamino-2propanols, RNHCH2CH(OH)CH2NHR1.127 They probed the reaction of N-alkylsulfamates with urea and formaldehyde128 giving 1-(N-alkylnitroaminomethyl)-3-nitroureas, RN(NO2)CH2NHCONHNO2, and with guanidine, nitroguanidine, H2NC(NNO2)NH2, 3,4-diaminofurazan, and 3-amino-4methylfurazan129 giving various nitroproducts, for example, nitroguanidine gave H2NC(NNO2)NHCH2N(NO2)Me. Reaction of aliphatic amines with N-alkylsulfamates and form-

O 2NOCH 2 (CH 2) n N(NO 2)CH2 N(NO 2)CH 2(CH2 ) mONO2 , n,m = 1,2.134 These versatile hydroxyalkylsulfamates have also proved useful in synthesis of various heterocycles. N-Substituted aminomethyl1,4-dioxane 30 and 2,5-bis(aminomethyl)-1,4-dioxane 31 have been prepared in generally good yields by cyclization of the corresponding potassium N-[3-(2-chloroethoxy)-2hydroxypropyl]sulfamates 32.135 Cyclodehydration of potassium dihydroxyalkylsulfamates in concentrated H2SO4 gave 2-substituted morpholines and 1,4oxazepines,136 nitration of 2-hydroxyalkylsulfamates, and subsequent conversion of the nitroamines formed into ammonium salts followed by cyclization in methanolic alkali gave 4,5dihydro-1,2,3-oxadiazole 2-oxides 33137 in moderate yield and reaction of 2-hydroxyethylsulfamate and 2-substituted acetaldehydes gave rise to N-nitrooxazolidines 34.138 Dinitramidic acid and its ammonium salt have been prepared by nitration of ammonium sulfamate with fuming HNO3 using solid acid catalysts such as montmorillonite clay. Ammonium dinitramide, O2N−N −−NO2 NH 4+, is a replacement for ammonium perchlorate in solid propellants.139 This compound

aldehyde in HNO3 and acetic anhydride resulted in formation of 5-alkyl-1,3-dinitro-1,3,5-triazacyclohexanes 26 and linear nitramines 27 in reasonable yields.130 Nitration in HNO3/H2SO4 of Scheme 4. Reaction of 3-(ω-Haloalkoxy)-2hydroxypropylsulfamates with Amines and Ammonia

has also been prepared by nitration of potassium sulfamate, and it is claimed that this salt gives a better yield and purer product.140 Sulfamic acid has been used to prepare the surfactant ammonium dodecyl (lauryl) sulfate n-C12H25SO4−NH4+ by sulfating (O-sulfonation) of n-dodecanol in the presence of phosphinic acid at 130 °C for 1 h.141 A study of the naturally occurring sulfamates sarafloxacin 35 (R1 = R2 = H) and temafloxacin (R1 = Me; R2 = F) was carried out by plasma desorption MS, which gave protonated molecular ions.142

β-hydroxyalkylsulfamates gave β-nitroxyalkylnitramines, RN(NO2)CH2CH(ONO2)R,131 and nitration of the dinitroalkylsulfamates 28, obtained from reaction of gem-dinitroalkanes, RC(NO2)2CH2OH, and alkylsulfamates, gave the β-nitramino derivatives 29.132 Reaction of 3-(ω-haloalkoxy)-2-hydroxypropylsulfamates with amines or ammonia gave the corresponding diaminohydroxyethers, Scheme 4.133 Condensation of N-hydroxyalkylsulfamates with formaldehyde and subsequent nitration led to formation of N,N′-dialkylN,N′-dinitromethanediamines of general type

2.8. Sulfamate−Metal Bonds

Two different preparations of nickel sulfamate have been reported.143,144 The interdiffusion coefficients of aqueous nickel sulfamate solutions have been studied 1 4 5 , 1 4 6 The pentamminecobalt(III) complexes, [(NH3)5CoNHSO3]ClO4 and [(NH3)5CoNH2SO3](ClO4)2, have been investigated.147 Three papers from the same Ukranian group on copper(I) sulfamate π complexes report on the synthesis and crystal G


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structures of [((CH2CHCH2)2NCHO)Cu(NH2SO3)(H2O),28 Cu(4-allylthiosemicarbazide)]NH2SO3,29 and two copper(I) complexes with N-allyl derivatives of piperazinium sulfamate.148 A study of the synthesis of stannous sulfamate has been published.149 Preparation of some organotin sulfamates 36 and their thermal decomposition at 70 °C in benzene to give the vinylbutyltin compounds, Bu3SnCRCR1R2, in yields of 42− 95% has been investigated.150 Sodium sulfamate has been used to remove organotin compounds.151

degradation products using anion exchange HPLC and an anion suppressor.171 A HPLC assay method has been developed for the important dual-acting estrone sulfatase inhibitor SR 16157 (see section 5.2) currently in clinical trials for use in breast cancer therapy.172 Two papers deal with determination of the three well-known sulfa sweeteners, i.e., sodium cyclamate, sodium saccharin, and acesulfame-K.173,174 One method involves ultrasonic treatment followed by liquid chromatography-MS,173 and the second method is spectrophotometric and requires several chemometrics methods to resolve overlapping information on the three sweeteners.174 Cyclamate alone has been determined using headspace single-drop microextraction and GC with FID. The method works well and is free from interference effects.175

[Bu3SnCr(OSO2 N−CO2 CH3)CHR1R2⎤⎦Et3N+H 36

The synthesis, properties, IR spectra, and X-ray diffraction of the neptunium(V)-coordinated compound NpO2(SO3NH2)· H2O have been investigated.152 Quantum chemical simulations of iridium(IV,III) sulfamate aqua complexes and the mechanisms of their activation in electrochemical processes of metal deposition on gallium arsenide have been reported.153

2.10. Industrial Aspects

A short review in Chinese on the properties and applications of sulfamic acid (16 references) has appeared.176 A feature is inclusion of some physical data for about 20 sulfamate salts. The Institut National de Recherche et de Sécurité (INRS) issued a useful toxicology card (number FT209) detailing physical and chemical properties of sulfamic acid together with possible hazards and its use as well as storage and handling; there are 11 references included.177 A sulfamic acid manufacturing process involving oleum sulfurization of urea has been improved giving simplified technology, reduced sulfuric acid use, and improved yield and quality of product.178 Two reports discuss the synthesis of sodium cyclamate.179,180 The sulfurous acid salt Na2S2O5 in ice water was reacted with cyclohexylamine and worked up to give a 78% yield of Ncyclohexylammonium N-cyclohexylsulfamate,179 and in a second report the technology for synthesis of sodium cyclamate was improved using a 1:2.5:3.5 ratio of sodium sulfamate to cyclohexylamine to light oil, which gave an impressive 98% yield.180 Sulfamic acid derivatives have been used for many years as fire retardants, and two new compounds have been synthesized for this purpose. Aminotriazine sulfamate is used in a complex mixture to give an effective fire-resistant material,181 and the sulfamate phosphazene, R1(O)3PNSO3R1, R1 = ethercontaining C1−10 alkyl, haloalkyl, is used as a flame retardant in battery electrolytes.182 Hydrolysis of guanidine sulfamate gives guanidine ammonium sulfate183 and molten mixtures of acetamide−ammonium sulfamate give ammonium sulfate and acetonitrile.184 An ethylene oxide−sodium sulfamate adduct was used with monomers such as (HOCH2)2CHNHSO3Na and (HOCH2CH2)2NSO3Na in the preparation of polyurethanes

2.9. Analytical Aspects

The accuracy of the measurement by coulometric titration of sulfamic acid has been reported.154 Spectrophotometric determination of sulfamic acid involving first hydrolysis to ammonium sulfate and then a Berthelot reaction has been reported. The relative standard deviation of the results was 2%.155 Ion chromatography using a hydrophilic polymethacrylate and a quaternary ammonium radical was used to determine sulfamic acid in fertilizers.156 Isotope dilution electrothermal vaporization inductively coupled plasma MS has been used to determine metal impurities in sulfamic acid.157 In the singlecolumn ion chromatography of ammonium and alkali ions and alkylamines sulfamic acid has been found to be much superior to other strong acids.158 In both the spectrophotometric and the electrochemical determination of chlorine dioxide in the presence of Cl2 or Br2 sulfamic acid removed these and made the process efficient.159 Sulfamic acid was found to have high sensitivity and reasonable signal stability in EPR dosimetry studies.160 Sulfamic acid minimized interference in the procedure for determination of arsenic by hydride generation in AAS.161 Historically determination of either nitrite or sulfamic acid by reaction of both has been important, and several papers that use this reaction in analysis have appeared during the last 20 years or so. Reduction of nitrous acid by an aqueous solution of sulfamic acid for treatment of NOx gases has been described,162 and determination of DO in water containing high concentrations of nitrite was determined by sulfamic acid.163 Formation of N2 from nitrite and sulfamic acid was the basis of the method for isotope ratio analysis of soil extracts containing 15 N-labeled nitrite and nitrate,164 and the same reaction has used in colorimetric determination of sulfamate ions in water.165 An interesting application with sulfamic acid-doped aniline (PANISFA) in determination of nitrite was reported.166 The anticonvulsant drug topiramate 10 has been determined from the degradation products sulfate and sulfamate, formed in stoichiometric amounts, by capillary electrophoresis.167 A chemiluminescent nitrogen detector using reversed phase HPLC has been employed for determination of topiramate,168 and reversed phase HPLC was again used in work from another laboratory involved in topiramate analysis.169 An ion chromatography method with indirect UV detection has been used to determine topiramate from its degradation products, sulfamate and sulfate.170 Topiramate was again assessed from its

and polyesters.185 The system polyamide/sulfamate/dipentaerythritol as a flame retardant has been looked at, and use of sulfamates and other sulfur compounds as flame retardants has been reviewed.186 Synthesis of 1,3,4-oxadiazoles and poly(1,3,4oxadiazole-2,5-diyl-1,4-phenylene) uses sulfamic acid or/and its salts.187 Poly(sulfamate−carboxylate)isoprene 37 has been prepared using chlorosulfonyl isocyanate, ClSO2NCO.188 Sulfamic acid usage as a sulfating agent (O-sulfonation) has been reviewed briefly (in Chinese) with 22 references.189 H


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liquid and sulfamic acid219 would appear to be contemporaneous with the claim above.215

Conversion of n-dodecanol to n-dodecyl-(lauryl)sulfate has been done with sulfamic acid.141 Sulfonation of cobalt phthalocyanine to give cobalt phthalocyaninetetrasulfonic acid is carried out with sulfamic acid,190 and synthesis of 2-amino-5-methoxybenzenesulfonic acid was carried out with sulfamic acid and panisidine.191 Some aminobenzenesulfonic acids have been prepared using sulfamic acid, for example, when 2-aminobenzonitrile was reacted with sulfamic acid in sulfolane at 130− 140 °C for 3 h a 74% yield of 4-amino-3-cyanobenzenesulfonic acid was obtained.192 3-Hydroxy-2-imino-1(2H)-pyridinesulfonic acid was prepared from furfural and sulfamic acid.193 Electrochemical oxidation of sulfamic acid gave azidodisulfonate ions.194

MeCOCH 2COOR1 → MeCOCH 2COOR2

Sulfamic acid has also found use in preparation of substituted αamino acids, such as p-hydroxyphenylglycine.220 Recently, silica-bonded N-propylsulfamic acid, nPrNHSO3H, has found application in formylation and acetylation of more than 20 alcohols, phenols, and amines with generally excellent product yields.221 Control experiments showed that while sulfamic acid alone gave 45% yield the silica-bonded material gave up to 92% yields. The same silica catalyst has been used for transesterification of soybean oil with MeOH.222 Silicasupported sulfamic acid has been employed as a cost-effective catalyst for peracetylation of carbohydrates with excellent yields.223 2.11.2. Ethers, Acetals, Ketals, and Anhydrides. Acetolysis of cyclic ethers, such as THF, in the presence of sulfamic acid gave generally excellent yields of diacetoxyalkanes, e.g., MeOCO(CH2)4OCOMe, from THF.224 Mild procedures with sulfamic acid as catalyst have been used to protect carbonyls

2.11. Sulfamic Acid and Sulfamates as Catalysts

A 30 page review (in Chinese) has appeared covering “salt-type organic acids: a class of green acidic catalysts in organic transformations”,195 and the same worker has a shorter 2 page review with 21 references highlighting the major applications of sulfamic acid as a catalyst.196 2.11.1. Esters. Sulfamic acid has been used as a solid catalyst for preparation of a number of acetates. Esterification of acetic acid with n-BuOH gave a 78% yield of the ester after 1 h,197 and iamyl alcohol gave 89% i-amyl acetate after 2 h refluxing at 140− 150 °C.198 Twenty acetates of alcohols and phenols have been made in >90% yields using sulfamic acid with acetic anhydride in a chlorinated solvent.199 Ethyl benzoate (87% yield),200 phenyl benzoate (73% yield),201 benzyl propionate (95% yield),202 and methyl 1-naphthylacetate (98% yield)203 have all been reported in reactions employing sulfamic acid as catalyst. Preparation of a new reactive surfactant methyl ricinoleate 38 using sulfamic acid has been described.204 Two papers report >80% yields of n-butyl chloroacetate, ClCH2CO2Bu, using sulfamic acid as a catalyst.205,206 In very recent work an Indian group used sulfamic acid for acylation and sulfation of carbohydrates under solvent-free conditions207 and for glycosylation of D-glucose, D-mannose, Dgalactose, L-rhamnose, and N-acetyl-D-glucosamine.208 Regioselective esters of amylose have been prepared with sulfamic acid as the catalyst.209 Various diesters of diprotonic acids have been prepared using sulfamic acid as catalyst. Two separate reports have shown that dibutyl maleate, BuOCH2CHCHCH2OBu, can be obtained in >94% yield,210,211 dimethyl fumarate, MeO(CO)CH CH(CO)OMe, in 90% yield,212 and di-n-butylphthalate in 89% yield.213 Fifteen aldehydes either neat or in dichloromethane solvent have been converted (>90%) to their 1,1-diacetates, RCH(OAc)2.214 A similar result has been achieved using the ionic liquid [bmim]PF6 in conjunction with sulfamic acid, and this is stated to be the first report where sulfamic acid has been used with ionic liquids in synthetic chemistry.215 Tri-n-butyl citrate has been made from citric acid and nbutanol with sulfamic acid as catalyst,216 and acetyl tri-n-butyl citrate, BuOCOCH2C(OAc)(CH2OCOBu)2 has also been synthesized again with sulfamic acid as catalyst.217 Cyclic olefins react with aliphatic acids in the presence of sulfamic acid to give excellent ester selectivity and fair to very good yields of product in the 12 reactions reported.218 1-Propyl-3-methylimidazolium chloride, [C3MIm]Cl, ionic liquid together with sulfamic acid were used as a chemoselective catalyst for transesterification of β-ketoesters. This use of an ionic

forming acetals and ketals in good yields.225,226 Cyclohexanone 1,3-butanediol ketal (94% yield), 39, and benzaldehyde 1,2propanediol acetal (95% yield), 40, have been synthesized using sulfamic acid catalyst.227,228 Reaction of cyclohexane glycol ketal 41 from cyclohexanone, glycol, and sulfamic acid has been studied kinetically229 Two groups synthesized dibenzalpentaerythritol 42 using sulfamic acid.230,231 In one case microwave irradiation without solvent was used.231 N-Benzyloxycarbonyl-Laspartic acid reacting with Ac2O gave the anhydride 43 in the presence of sulfamic acid.232 2.11.3. Aldehydes and Ketones. Several Mannich reactions have been carried out successfully with sulfamic acid as catalyst. A direct 3-component reaction with acetone, aldehydes, and anilines led to β-aminobutanones in high yields.233 A similar type of reaction using ultrasound irradiation also produced high yields,234 and 60−95% yields were found in the Mannich reaction of cyclohexanone or 3-pentanone or aromatic ketones with aromatic aldehydes and amines.235 Large-scale preparation (∼50 times laboratory scale) of various β-amino carbonyl compounds was achieved using aniline, acetophenone, and benzaldehyde in a Mannich reaction with sulfamic acid.236 Preparation of 1-acyloxy-3-halo-2-propanones, XCH2COCH2CO2R,237 and β-acetamido ketones such as 1,3[PhCOCH2CH(NHAc)]2C6H4238 again with the agency of sulfamic acid as catalyst have been reported. Sulfamic acid is an I


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effective catalyst for reaction of β-diketones with arylamines to give β-enaminones in high yield.239 Allylation of aldehydes by nucleophilic addition with allyl nbutylstannane, CH2CHCH2SnBu3, in the presence of sulfamic acid gave the corresponding homoallylic alcohols in high yield, e.g., with benzaldehyde, PhCH 2 (OH)CH 2 CHCH 2 , formed.240 Crossed-Aldol reactions have been carried out with aromatic aldehydes and ketones with sulfamic acid present.241 Good yields of derivatives of 5-arylidene barbituric acid have been produced from aromatic aldehydes, barbituric acid, and sulfamic acid.242 2.11.4. Amides, α-Aminonitriles, and Amines. Beckmann rearrangement giving amides from ketoximes, R1R2CH NOH, in the presence of sulfamic acid in dry ACN gives reasonable to very good yields.243 p-Hydroxybenzoic acid, urea, and sulfamic acid give 77% p-hydroxybenzamide in 2 h at 230 °C.244 1-Amidoalkyl-2-naphthols have been made by 3component condensation of 2-naphthol, ureas/amides, and aldehydes in the presence of sulfamic acid under ultrasound irradiation.245 An efficient method has been developed for synthesis of N,N′-alkylidine bis-amides such as p-NO2C6H4CH(NHCOC6H4Cl-o) using sulfamic acid.246 Bis(triphenylphosphine) copper(I) tetrahydroborate, Cu(PPh3)2BH4, sulfamic acid, and amine provide direct reductive amination for aldehydes and ketones giving, for example, PhCH2NHPh from benzaldehyde and aniline.247 Three preparations of α-aminonitriles have been published.248−250 In the first sulfamic acid was functionalized on magnetic Fe3O4 nanoparticles forming a novel organic− inorganic hybrid heterogeneous catalyst which was then used in a 3-component reaction of aldehydes or ketones, amines, and trimethylsilyl cyanide to form α-aminonitriles.248 Trimethylsilyl cyanide was again employed with normal sulfamic acid and the reactant aldehydes and amines in the other two synthesis of αaminonitriles249,250 N-Boc protection of structurally diverse amines was achieved with sulfamic acid and (Boc)2O at room temperature under solventless conditions, giving yields of 90−100%.251 The 3-component synthesis of homoallylic amines using sulfamic acid, aldehydes, anilines, and allyltributylstannane gave yields of 80−90% of the products.252 Ring opening of epoxides with sulfamic acid and some heterocyclic amines and anilines in

Friedel−Crafts alkylation of indoles with benzyl alcohol and α,β-unnsaturated carbonyl compounds such as cyclopent-2enone with sulfamic acid gave good yields.257 There are four reports on the synthesis of bis-indolemethanes 45,258−261 and the first three are very similar employing indoles with aldehydes/ ketones and sulfamic acid. The last report uses chromic(III) sulfamate as the catalyst for conversion of indole to 45.261 A large number of pyrimidine systems have been synthesized via use of sulfamic acid or sulfamates as catalysts. 3,4Dihydropyrimidin-2(1H)-ones 46 were made in >80% yields with chromic(III) sulfamate in a Biginelli reaction using ethyl acetoacetate or acetylacetone, aldehyde, and urea.261 There are eight further reports dealing with synthesis of 3,4-dihydropyr-

imidin-2(1H)-ones in Biginelli reactions. Ultrasound radiation and sulfamic acid gave very good yields of 46;262 with sulfamic acid as catalyst both the pyrimidine−ones and the pyrimidine− thiones (using thiourea instead of urea) could be made in good yield,263 and use of zinc sulfamate proved innovative in the same reaction.264 In three other papers both the pyrimidine−ones and the pyrimidine−thiones have been made265−267 using copper(II) sulfamate in one case265 and sulfamic acid in the other two reports.266,267 In another paper with sulfamic acid yields and selectivities are given for the Biginelli reaction leading to type 46 compounds.268 1,2,3,4-Tetrahydropyrimid-2-ones have been synthesized in good yields using microwave irradiation and zinc sulfamate.269 Several more complex pyrimidines have been synthesized using Biginelli-type reactions. 5-Ethoxycarbonyl-4-(2-furyl)-6methyl-3,4-dihydropyrimid-2(1H)-one 47 was made using sulfamic acid and ultrasonic irradiation in a 3-component Biginelli reaction.270 4-Phenyl-6-methyl-5-ethoxycarbonyl-3,4dihydropyrimidin-2(H)-one was synthesized using sulfamic acid

in aqueous EtOH and benzaldehyde, urea, and ethyl acetoacetate.271 4,6-Diarylpyrimidin-2(1H)-ones have been prepared with sulfamic acid, acetophenone, aldehydes, and urea,272 and the same group prepared the novel fused pyrimidine systems, chromeno[4,3-d]pyrimidine-6-one, triazolo[1,5-a]pyrimidine-5-one, and pyrido[2,3-d]pyrimidine-2,4,7-trione, again using sulfamic acid.273 A 3-component reaction of aldehyde, β-dicarbonyl compound, and 2-aminobenzimidazole with sulfamic acid present gave benzo[4,5]imidazo[1,2-a]pyrimidine.274 N-Alkyl-imides 48 and N-aryl-imides 49 have been prepared from succinic and phthalic anhydrides, respectively, by reaction with amines in the presence of sulfamic acid.275 Several pyrazole derivatives have been synthesized, all employing sulfamic acid as catalyst.276−279 Thus, synthesis of various benzochromeno-pyrazoles276 and pyrano-pyrazoles277 have been reported by the same group. For synthesis by the latter two routes were used: one with sulfamic acid in ACN and the

solventless conditions gave an easy route to β-aminoalcohols in ∼90% yields.253 2.11.5. N-Heterocycles. Paal−Knorr condensation of 2,5hexanedione with primary amines and a catalytic amount of sulfamic acid gave good yields of N-substituted pyrroles.254 Synthesis gives very high yields of pyrrole, furan, and thiophene derivatives in the presence of sulfamic acid from 1,4-diketones and amines, [bmim]BF4 and H2S, respectively.255 Sulfamic acidcatalyzed Michael addition of pyrrole and indoles to nitroolefins under solvent-free conditions has been described.256 For example, pyrrole and PhCHCHNO2 gave the Michael adduct 44. J


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second without sulfamic acid but using microwave irradiation.277 6-Amino-4-aryl-3-methyl-1-phenyl-1,4-dihydropyrano[2,3-c]pyrazole-5-carbonitriles 50 were synthesized via a one-pot 3component reaction with sulfamic acid in EtOH.278 Yields vary aldehydes, and Meldrum’s acid, i.e., 2,2-dimethyl-1,3-dioxane4,6-dione at 120 °C without solvent.294 Solvent-free synthesis with sulfamic acid has led to the related [1,3]-dioxolo[4,5b]xanthen-9-ones 57 and in the same reaction as benzo[a]xanthen-11-ones 58.295 Synthesis of aryl-14H-dibenzo[a,j]xanthenes 59 using microwave irradiation and sulfamic acid has been carried out very successfully (yields >90%) in a solventfree system by condensation of β-naphthols with various aromatic aldehydes.296 Substituted coumarins 60 have been synthesized by the Pechmann reaction of phenols and β-ketoesters in the presence of sulfamic acid in a solvent-free system.297 Sulfamic acid has been employed in a solvent-free tetrahydropyranylation of 12 alcohols using 3,4-dihydro-2H-pyran giving products 61 in yields of >86%.298 2.11.7. O−N and S−N Heterocycles. One-pot synthesis in good yields of tetrahydroquinolines from aromatic aldehydes, anilines, and 2,3-dihydrofuran or 3,4-dihydropyran with sulfamic acid as catalyst has been described.299 Structurally diverse spiroheterocycles containing nitrogen and oxygen atoms in their

from 30% to 90% in the 3-component synthesis of various 1,4dihydropyridines containing a pyrazole ring 51.279 Two Friedlander quinolone syntheses have been reported.280,281 In the first α-aminoaryl- and α-methyleneketones undergo facile reaction in the presence of sulfamic acid to give excellent yields of polysubstituted quinolones.280 In the second report sulfamic acid heterogenized on hydroxyapatite-encapsulated γ-Fe2O3 nanoparticles was used.281 4-Aryl-3-methyl-1phenyl-1H-benzo[g]pyrazolo[3,4-b]quinolone-5,10-diones were made in a 3-component system with sulfamic acid.282 Two papers reported on the synthesis of quinoxalines 52 using sulfamic acid as the catalyst in each case,283,284 and there is a report on the synthesis of 2-substituted-2,3-dihydroquinazolin4(1H)-ones with sulfamic acid.285 Five papers have been published dealing with synthesis of diazepines. Two papers from the same group286,287 deal with 1,5-

benzodiazepines 53 synthesized from o-phenylenediamines and ketones with sulfamic acid as catalyst. Benzo-[b]-1,4-diazepines have been synthesized similarly with sulfamic acid present.288 Some thiadiazolo 1,5-benzodiazepines have been made in >70% yields using microwave irradiation and sulfamic acid.289 1,2,4,5Tetrasubstituted imidazoles 54 have been synthesized in good yields using silica-bonded propylpiperazine N-sulfamic acid.290 Benzimidazole derivatives substituted in both rings have been made in the presence of sulfamic acid in MeOH using ophenylenediamines and orthoesters.291 Another report substitutes the orthoesters with aromatic aldehydes leading to two types of benzoimidazoles.292 Potassium sulfamate with urea, guanidine, and 3,4-diaminofurazan with formaldehyde give a variety of heterocyclic nitramines, e.g., 55.293 2.11.6. O-Heterocycles. Silica-bonded N-propylsulfamic acid has again been used this time in the synthesis of 8-aryl7,8-dihydro-[1,3]-dioxolo[4,5-g]chromen-6-ones 56 in a 3component system with 3,4-methylenedioxyphenol, aromatic

ring systems such as spirotryprostatin A and B, horsfiline, gelsemine, and coerulescine have been made.300 Catalysis by sulfamic acid which initiates a multicomponent domino reaction of 2-aminobenzothiazoles with isatin and cyclic 1,3-diketones leads to these complex heterocyclic products. Yields with and without microwave irradiation are fairly comparable in the sulfamic acid-catalyzed synthesis of 3-(4,6-dimethyloxazolo[4,5c]quinolin-2-yl)-chromen-2-ones.301 Two other systems containing quinolone rings have been described. 4-Aryl-3-methyl-1phenyl-1H-benzo[g]pyrazolo[3,4-b]quinolone-5,10-diones K


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62282 and the polyhydroquinolines 63302 have been prepared using sulfamic acid as catalyst. The latter preparation involved a 4-component Hantzsch condensation reaction. β-Enaminoketone derivatives of 3-(2-oxo-2-arylethylidene)3,4-dihydro-1H-quinoxalin-2-ones and 3-(2-oxo-2-arylidene)3,4-dihydrobnzo[1,4]oxazin-2-ones were prepared in excellent yields using sulfamic acid as catalyst and o-phenylenediamine and o-aminophenol, respectively, with 2,4-dioxo-4-arylbutyrate.303 Substituted 1,3-oxazines 64 have been made in very good yields using sulfamic acid in a one-pot 3-component reaction of anilines, alkynoates RCO2CCCO2R, and formaldehyde.304 The fungicide thiabendazole 65 has been prepared in good yield using o-phenyldiamine and 4-cyanothiazole in the presence of sulfamic acid.305,306 Synthesis of novel tricyclic 2H-pyrimido[2,1-b]benzothiazoles has been carried out in a one-pot 3-component reaction with an aldehyde, β-ketoester, and 2-aminobenzothiazole in the presence of sulfamic acid.307 2.11.8. Polymers and Miscellaneous Reactions. Two papers on polyphosphazenes have appeared.308,309 Both sulfamic acid and ammonium sulfamate were used in reaction of poly(dichlorophosphazene) with sodium alkoxides or aryloxides giving the phosphazene polymers, [P(OR)2:N]n. Synthesis of polycyclic nitramines by nitration of the condensation products from reaction of glyoxal and formaldehyde with sulfamic acid salts has been reported.310 Preparation of N-sulfonylimines, RCHNSO2Ar, by reaction of arylsulfonamides, ArSO2NH2, sodium arenesulfinate, ArSO2Na, and aldehydes with sulfamic acid as catalyst in water−alcohol gave yields of 47−81%.311 Knoevenagel condensation of aromatic aldehydes and RCH2CN (R = CN, CO2Et, CONH2) in the presence of sulfamic acid under microwave irradiation gave >90% yields of arylidene compounds, ArCHC(CN)R.312 Catalytic (sulfamic acid) synthesis of diethanolamine, HO(CH2)2NH(CH2)2OH, was

Silica-bonded propyl-diethylene-triamine-N-sulfamic acid has been prepared from 68 and used for synthesis of 1,1-diacetates by reaction of aromatic aldehydes and acetic anhydride under solvent-free conditions.318 The catalyst was made from 68, 3diethylenetriamine-propylsilica, and chlorosulfonic acid in CHCl3. 2.12. Amine Sulfur Trioxide Adducts: R3N−SO3

2.12.1. Computational and X-ray Studies. A series of donor−acceptor complexes containing sulfur trioxide has been studied in the gas and condensed phases using DFT.319 Complexes MeNH2−SO3 and Me2NH−SO3 exhibit properties intermediate between the previously studied H3N−SO3 and Me3N−SO3. Two oxygen-containing complexes MeOH−SO3 and Me2O−SO3 have also been characterized for the first time. Rotational spectroscopy has been used to study the donor− acceptor complex C5H5N−SO3.320 The N−S bond length is 1.915(1) Å, and the NSO angle is 98.91(2)°. Binding energies have been determined for these complexes and also for the following: Me3N−SO3, H3N−SO3, MeCN−SO3, HCCN−SO3, and HCN. DFT calculations of nitrogen quadruple coupling constants for the SO3···B (Lewis bases; H3N−SO3, Me3N−SO3, HCN−SO3, C5H5N−SO3, MeCN−SO3, HCCCN−SO3, and (HCN)2SO3) correlated very well with experimental data from microwave spectroscopy.321 A microwave study of the structure, bonding, and dipole moment (7.1110(69) D) of Me3N−SO3 in the gas phase gave an N−S bond length of 1.912(20) Å and an NSO angle of 100.1(2)°.322 The crystal structure of trimethylsilyl N,N-dimesylsulfamate, (MeSO2)2NSO3SiMe3, has been determined, and a very long Si(sp3)−O bond and a short S(sp3)−O bond have been found. The sulfamate in water is immediately hydrolyzed to (MeSO2)2NH, sulfuric acid, and (Me3Si)2O, but it can also act as a sulfosilylating agent, and it reacts with various Lewis bases (B) to give B:SO3.323 The addition reaction of thiobismorpholine 69 and norborene in the presence of pyridine−sulfur trioxide gave rise to some interesting complex products including 70, the structure of which was determined by X-ray.324 2.12.2. N-Sulfonation. A minireview with 12 references highlighted some of the principal reactions that amine−sulfur trioxide adducts undergo.325 Three du Pont patents on sulfonation (C−SO3H), sulfation (O−SO3H), and sulfamation (N−SO3H) employing SO3 adducts in various supports such as silica, silicalite, zeolite, and others have been filed.326−328 Amino alcohols reacting with Et3N−SO3 in pyridine gave dihydroxy sulfamates, e.g., (HOCH2)2CHNHSO3Na, in 90% yield.329 Another route to a similar type compounds involves using ethylene oxide, sodium sulfamate, and KOH in xylene at 130 °C over 10 h, giving 96% yield of (HOCH2CH2)2NSO3Na compared to 40% when pyridine−sulfur trioxide was reacted with (HOCH2CH2)2NH.123 Other alkylene oxides may also be used. A chiral sulfamic acid, R1R2NSO3H, with at least one of the R groups being chiral was prepared by treating 2-amino-3-phenyl1-propanol with pyridine−sulfur trioxide. These sulfamic acids

achieved in 92% yield using a reaction time of 6 h and 140 °C.313 Ammonium salicylate and urea in the presence of sulfamic acid with magnesium oxide gave an 86% yield of o-hydroxybenzoniScheme 5. β-Aminoselenation of Alkenes with Selenamides

trile.314 Sulfamic acid and some alkylsulfamic acids have been used for synthesis of dihydric phenols (catechol, hydroquinone) starting from phenol and Me2CHCH2COMe or phenol and a ketone peroxide.315 α-Hydroxy-phosphanates 66316 and αamino-phosphonates 67281 have been synthesized using sulfamic acid and ultrasound irradiation in solvent-free conditions for the former and sulfamic acid heterogenized hydroxyapatiteencapsulated γ-Fe2O3 nanoparticles for the latter. β-Aminoselenation of alkenes with selenamides in the presence of sulfamic acid gives the 2-amino-1-phenylselenohexane (20%) and trans-amino selenide (65%), Scheme 5.317 L


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could be used to resolve PhCHMeNH2.330 Alkyloxazolines 71 react with trialkylamine−sulfur trioxide complexes such as Me3NSO3 to give Me3N+(CH2)2N(SO3−)CO(CH2)nMe.331 There are two reports on the use of amine−sulfur trioxide adducts for synthesis of the non-nutritive sweetener cyclamate. Using Et3N−SO3 under optimum conditions a yield of 95% was realized,332 and with dioxane−sulfur trioxide a comparable yield was reported.333 The hitherto unknown phosphoryl sulfamic acid, (EtO)2P(O)NHSO3H, has been synthesized by a Polish group by sulfamation of (EtO)2P(O)NH2 with DMF−SO3.334 Some interesting chemistry is also reported on. 2.12.3. O-Sulfonation. A relatively recent review on “chemical sulfation of small moleculesadvances and challenges” has a two-page section on sulfation using amine−sulfur trioxide complexes.335 Cis and trans or a mixture of both hydroxydioxanes 72 (R = H, p-MeC6H4-, Me(CH2)n- (n = 6, 8, 10)) were sulfated with pyridine−sulfur trioxide in CCl4/ pyridine giving 72 with R1 = SO3Na.336 Disaccharides with 4- and 6-sulfate and 4,6-disulfate groups have been synthesized with Me3N−SO3 to give β-D-GlcA-(1→3)-β-D-Gal disaccharides with sulfate groups in place.337 About 90% sulfation of glycosides with pyridine−sulfur trioxide can be achieved. Thus, n-dodecyl laminaripentaoside at 84 °C gave 94% sulfation.338 Polygalactosoamines can be sulfated with pyridine−sulfur trioxide.339 Lignins have been sulfated successfully at pH 11 in 50% NaOH at 90 °C using Me3N−SO3.340 Sulfonated cellulose used as a carrageenan substitute was manufactured by reacting DMF− sulfur trioxide at −5 to 100 °C.341 The same adduct sulfur trioxide complexes were found to be more suitable than the more commonly used pyridine−sulfur trioxide adduct for tyrosine sulfation.342 Two tyrosine−sulfate-containing peptides were synthesized in this way. Formamide−sulfur trioxide at 25−55 °C under dry N2 gas sulfonates dextran in good yield and high purity.343 3-Hydroxyestra-1,3,5(10)-trien-17-one in THF treated first with MeONa at −10 °C and then with pyridine−sulfur

lithiums is a general and an efficient way (yields from 60% to 79%) of making aliphatic and aromatic sulfonic acids.349 Addition of the −OSO3 group occurs when N,N-dimethylaniline-N-oxide reacts with pyridine−sulfur trioxide giving the osulfated product 75 after the initial product 76, which was not isolated, was treated with water.350 The author criticizes an earlier report of Edward and Whiting351 because they clearly say that 76 does not rearrange to 75. However, Edward and Whiting did make 76 and it did not rearrange to 75 under their conditions, whereas in this more recent report the author started from the N,N-dimethylaniline Noxide and got 75 possibly via the intermediacy of 76. Further carefully designed experimental work is needed to clarify the position. It is quite possible that both authors are correct and that under certain conditions 76 will rearrange to 75. Sulfur trioxide in CH2Cl2 inserts into RRNCl (R = piperidino, morpholino, diethylamino) at room temperature giving 90−98% RRNSO2(O)Cl.352 Aminoselenylation of cyclohexene with PhS−NEt2 in the presence of sulfamic acid gave, after treatment of the initial product with 10% HCl, trans-2-phenylthiocyclohexylamine 77.353 Thermal decomposition of the adducts formed by arylamines and SO3 (as SO3 sorbents) occurred in two stages: SO3 loss at 70−150 °C and amine boiling at 120−260 °C.354 2.13. N-Sulfonylamines

A review that deals with some of the earlier material on Nsulfonylamines came out over 25 years ago but is useful for references.355 MNDO studies on HNSO2 and some related species, HNCS, HNSO, H2CCS, and H2C SO2, at the MNDO and MINDO/3 levels of theory have been reported.356 MINDO/3 and AM1 calculations on HNSO2 and MeNSO2 have given enthalpies of formation, ionization potentials, dipole moments, and atomic charges. Data are also calculated for the less stable thiocarbonyl dioxides, RRC SO2.357 Gas-phase reaction of NH2− and SO2F2− gives NSO2 − (85%) and HNSO2F−(15%). NSO2− is the conjugate base of

trioxide at 0 °C gave 3-sulfatoxy estra 1,3,5(10)-triene-17-one as the sodium salt.344 2.12.4. C-Sulfonation and Miscellaneous Reactions. Quinoline-5- and quinolone-8-sulfonic acids have been prepared using liquid SO3 added dropwise and at ≤40 °C and heating the mixture at 150 °C for 2 h giving 80.4% for the first acid,345 and heating at 180 °C for 2 h gave 67% of the second sulfonic acid.346 The mechanism of the ring sulfonation of anilines is illustrated in 73 and involves electrophilic attack by a sulfur trioxide dimer, S2O6, on the unprotonated aniline molecule leading to mainly para-C-sulfonation.347 The betaine 1-(sulfonatomethyl)-3-(N-pyridinium)adamantine 74 formed when 3,7-dimethyenebicyclo[3.3.1]nonane reacted with pyridine−sulfur trioxide.348 Insertion of SO3 with Me3N−SO3 into metal−carbon bonds of organo-

HNSO2, and both species are implicated as intermediates in reactions of sulfamate esters.358 Ab initio calculations have been done on NSO2−. Calculated and experimental electron affinities for NSO2− are in excellent agreement. Gas-phase studies with FT-ICR gave ΔH°acid =1381 ± 221 kJ/mol for HNSO2 at 333 K. Though not measured a high gas-phase acidity is expected for HNSO2. There is some interesting evidence for the HNSO2 species hidden in a 1987 German paper.359 The MS of the molecular ion from compound 78 is 276, and one of the other M


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Scheme 6. Thionitrosobenzene with Oxygen Gives an NSulfonylamine Followed by 1,3-Dipolar Addition

present.372 Radiolysis of R1R2NSO2Cl in 2-methyl-THF or Me4Si gave sulfamoyl radicals R1R2NSO2• and other radicals such as R1R2N•.373 2.14.2. NH2SO2Cl and N-Monosubstituted Halides. An important improvement in the sulfamation reaction was achieved some years ago by Okada by the judicious choice of solvent.374

fragments has a mass of 197the difference 79 corresponds exactly to the mass of HNSO2. The N-sulfonylamines RNSO2 (R = tBu, Me, Me(CH2)2, Me2CH, and Me2CHCH2) were made from the corresponding sulfamoyl chlorides and reacted with diazo compounds, RCH N2, to give thiadiaziridine 1,1-dioxides 79 in yields averaging 40%.360 The thionitrosobenzene 80 reacts with oxygen to give a putative N-sulfonylaniline, which undergoes an interesting intramolecular 1,3-dipolar cyclization giving 81 (Scheme 6), and this is the first example of such an addition involving Nsulfonylamines.361 N-Sulfonylamines have been invoked in

For sulfamoylation with NH2SO2Cl of a variety of alcohols and phenols use of DMA or 1-methyl-2-pyrrolidone as solvent accelerated the reaction considerably and gave excellent yields.375 Substrates p-HOC6H4COMe, p-HOC6H4OMe, and C6H5(CH2)3OH and more complex structures such as 84 were all sulfamoylated. Sulfamoyl chloride has been used for preparation of 3α-sulfamate and 3β-sulfamate derivatives of steroids to give compounds such as 20-oxo-5α-pregan-3α-yl sulfamate and the 3β-yl sulfamate, etc.376 Sulfamoyl chloride 85 has been used to prepare N-alkylsulfamides,377 and the sulfamoyl chloride 86 has also been used to synthesize medicinally important benzothiadiazine sulfamides.378 Okada’s use of DMA has been put to use industrially to synthesize 93% 17-oxoestra-1,3,5(10)-triene-3-yl (sulfamoylated 84 at the OH).379 Reaction of i-propylsulfamoyl chloride with methyl anthranilate gave 96% of the herbicide bentazon 87.380 The phosphorus-containing sulfamoyl chloride Ph3PNSO2Cl has been prepared by reaction of sulfamic acid with Ph3PCl2, and the procedure has been checked.381 The ionic liquid 1-butyl-3-methylimidazolium chloroaluminate [bmim]Cl·AlCl3 and the sulfamoyl chlorides X−SO2Cl (X = Et2N, (nBu)2N, and C5H10N) were reacted with a range of arenes giving various pharmaceutically important sulfonamides.382 2.14.3. N,N-Dimethylsulfamoyl Halides. Manufacture of N,N-dimethylsulfamoyl chloride from Me2NH and SO2Cl2 in 1,2-dichloroethane at 10−20 °C giving 96% yield has been patented.383 Preparation of sulfamoyl chlorides by reaction of R1R2NH (R1 = alkenyl, alkynyl, haloalkenyl, etc., and R2 = alkyl, alkenyl, and alkynyl) with sulfur trioxide in the presence of phosphorus chlorides has also been the subject of a patent.384 The type of chloride made is typified by CH2CH−CH2N(nPr)SO2Cl. Another route to sulfamoyl chlorides involves reaction of dimethylchloramine Me2NCl with SO2, which gave 70% N,N-dimethylsulfamoyl chloride product.385 Regioselective protection of 4-iodoimidazole with N,Ndimethylsulfamoyl chloride and 50% aqueous NaOH in THF gave 97% N,N-dimethyl-4-iodoimidazole sulfamide 88.386 The reaction includes the interesting rearrangement of 88 to the

several papers involving hydrolysis and aminolysis (Et2NH, pyridines, quinuclidines, anilines, and cyclic amines) of sulfamate esters.362−365 A series of six N-sulfonylamines RNSO2 (R = iPr, tBu, Bz, cinnamoyl (E), CO2Me, and CO2Et) synthesized from the corresponding sulfamoyl chlorides have been reacted with 3dialkylamino-2H-azirines to give 5-membered sulfamide heterocyclics.366 N-Sulfonylamines RNSO2 (R = Me, Et, iPr, and tBu) have been trapped with 3-trimethylsiloxy-1,3-butadiene, CH2CH-C(OSiMe3)CH2, to give the [2 + 4] adduct 82. The sulfonylamines Et (or Me)NSO2 reacted with 2-aza-1,3dienes, R1CH2C(Ph)NC(Ph)CHR1, to give 83.367 N-Sulfonylmethylamine inserts into the sulfenamides ArSNR2 to give N-arylthiosulfamides, ArSN(Me)−SO2−NR2, in yields from 42% to 79%.368 The N-sulfonylamines, RNSO2 (R = Me, Me3C), react with R′2NCH2NR′2 to give the sulfamides R′2NCH2N(R)SO2NR′2 and R′2NSO2NHR.369 2.14. Sulfamoyl Halides and Azides

2.14.1. Physical Studies. Vibrational studies of N-sulfamoyl chloride have been reported using IR and Raman spectroscopy accompanied by DFT calculations.370 The main conformer possesses an anti conformation (Cs symmetry with the S−Cl single bond in an anti position). The same group extended their studies to examine N-sulfamoyl fluoride and N-(fluorosulfonyl)imidosulfuryl fluoride, F2S(O)NSO2F, using FT-IR and Raman spectroscopy and DFT calculations. Again, the main conformer of sulfamoyl fluoride possesses the anti conformation, and the sulfuryl fluoride has a single conformation with C1 symmetry.371 The three sulfamoyl halides NH2SO2X (X = F, Cl, and Br) have been studied theoretically using DFT-B3LYP/6-311G** and ab initio MP2/6-311 + G** calculations. The molecules were predicted to exist mainly in the anti form, and for the fluoride about 98% anti and 2% syn were calculated to be N


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Dimethylsulfamoyl chloride reacts with 2-methylbenzenesulfonamides, 2-MeC6H4SO2NHAr, to cause cyclization, giving 2,3dihydro-1,2-benzothiazoles 92 in moderate yields in most cases.397 The same group showed that the same chloride can react with sulphonamide 93 in the presence of tert-butyllithium and TMEDA giving 2,3-dihydro-1,2-benzisothiazole 1,1-dioxides 94.398 A very practical synthesis of sulfonamides from dimethyl-, diethyl-, and piperidinylsulfamoyl chlorides and aromatics such as toluene, anisole, naphthalene, and chlorobenzene in the presence of indium triflate, In(OTf)3, as catalyst gives simple sulfonamides ArSO2R with R = NMe2, NEt2, and NC5H10).399 Dimethylsulfamoyl chloride reacted with 1,6-dimethyl-8αaminoergoline, giving 6-dimethyl-8α-(N,Ndimethylsulfonamide)ergoline.400 Sulfamide Me2NSO2NHOCH2Ph was prepared in the reaction of Me2NSO2Cl with NH2OCH2Ph,401 and a similar type of sulfamide Me2NSO2NHOEt was prepared by adding dimethylsulfamoyl chloride to a solution of NH2OEt with DMAP in pyridine at 40−50 °C.402 3-[3-(Sulfamido)-4-

isomeric 89. Reaction between dimethylsulfamoyl chloride and some 2,3-disubstituted imidazoles in Et3N in refluxing toluene gave N,N-dimethyl-N′-substituted imidazole sulfamides.387 Reaction of 2-aminomethyl-4-tert-butyl-6-iodophenol, protected with (CF3CO)2O, with dimethylsulfamoyl chloride resulted in formation of the sulfamate ester 90 following deprotection.388 When dimethylsulfamoyl chloride and a terminal olefin, RCH CH2 (R = nBu, n-hexyl, and n-octyl), in methylene chloride was irradiated with a tungsten lamp in the presence of s-butylbis(dimethylglyoximato)pyridinecobalt(III) and s-BuCo(dmgH) 2py sulfonamide products, Me2NSO2CH2CHClR formed.389 The sulfamide 91 formed when dimethylsulfamoyl chloride was reacted with 2-tert-butyl-1-(cyclohexylmethyl)-N-methyl1H-benzimidazol-5-ylamine.390 R2NSO2Cl (R = Me, Et) reacts with isoquinoline and indole to give a sulfamide that combines the isoquinoline and indole rings.391 Two Japanese patents392,393 described the use of dimethyl- and bis-dimethylsulfamoyl chlorides in reaction with substituted triazoles to prepare fungicides that incorporate the triazole ring(s). Dimethylsulfamoyl chloride reacts with N,N-dimethylamines with catalytic amounts of DMAP present and RCO2H and ROH producing carboxylic esters and amides, respectively, in excellent yields.394 Two mechanistic papers appeared which deal with solvolysis of N,N-dimethylsulfamoyl chloride. In the first paper395 use of

Scheme 7. Preparation of N-Fluorosulfonylazoles by Reaction of Azole Substrates with FSO2ONF2

cyanophenyl]-6-trifluormethyluracils 95 showing potential as herbicides have been made from dimethylsulfamoyl chloride and a suitable precursor.403 Iminium salts 96 made from 4-

dialkylaminopyridines and dimethylsulfamoyl chlorides are used in agrochemical fungicides.404 2.14.4. Sulfamoyl Fluorides. Eight arylsulfonamides ArSO2NH2 with various p-, o-, and 3,5-substituents react in generally good yields with p-trifluoromethylphenyl(difluoro)-λ3bromame F3CC6H4BrF2, giving the corresponding sulfamoyl fluorides ArNHSO2F.405 More than 10 N-fluorosulfonylazoles have been prepared by reaction of O-fluoro-N,N-difluorohydroxylamine FSO2ONF2 with azole substrates schematically shown in Scheme 7. Both phase transfer and homogeneous conditions were used for synthesis.406,407 Further reaction of the new compounds with lithium azoles gives rise to N,N′-sulfonylbis-azoles 97. Synthesis of ammonium imidobis(sulfonyl fluoride), NH4N(SO2F)2, as solid crystals in 97% yield by reaction of NH3 in CFCl3 with HN(SO2F)2 was reported some years ago.408 A number of (polyfluoroalkyl)sulfamoyl fluorides have been prepared by reaction of dimethylsulfamoyl fluoride over CoF3 at 300 °C, giving bis(trifluoromethyl)sulfamoyl fluoride, (F3C)2NSO2F (∼10%), bis(difluoromethyl)sulfamoyl fluoride (53%), (F 2 CH) 2 NSO 2 F (∼10%), (difluoromethyl)(trifluoromethyl)sulfamoyl fluoride, (F2CH)(F3C)NSO2F, and (difluoromethyl)(fluoromethyl)sulfamoyl fluoride (F2CH)(FCH2)NSO2F.409 This group patented an electrochemical process for preparation of the same and similar (fluoroalkyl)sulfamoyl fluorides using alkylsulfamoyl halides or alkylsulfamate derivatives with HF at a Ni electrode.410 Electrochemical fluorination of NH2SO2F gave rise to SO2F2, NF3, N2, and

the extended form of the Grunwad−Winstein equation points to an S N2 pathway with contributions from both solvent nucleophilicity and solvent ionizing power, and in the second paper396 the focus is mainly on phosphorus chlorides, but some data on Me2NSO2Cl is included. O


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traces of N2F2.411 Very good yields of polyfluoroalkylsulfamate diesters, HN(SO2ORf)2, were obtained by reacting HN(SO2Cl)2 with the fluoroalcohols RfOH (Rf = F3CCH2, F3CF2CCH2, F2CHF2CCH2, and (F3C)2) in refluxing benzene.412 In the

They can react with alkynes with CuTC catalyst in toluene to give 1-sulfamoyl-1,2,3-triazoles (Scheme 8). Intramolecular C−H amination has been carried out with azides in the presence of metalloradical cobalt(II) complexes of porphyrins leading to 1,3-diamines (starting from the appropriate monoamines) (Scheme 9). Formation of the intermediate

reaction of HN(SO2Cl)2 with HOCH2(CF2)4CH2 a polymer of molecular weight 4300 forms. Scheme 8. Reaction of Sulfamoyl Azides with Alkynes Giving 1-Sulfamoyl-1,2,3-triazoles cyclic sulfamides is excellent in the numerous reactions carried out.417 Reaction of the nucleoside 5′-sulfamoylazide 99 with the 3′hydroxy function of a protected nucleoside gave a sulfamatelinked dimer 100 which is resistant to EcoR1 cleavage.418 N(Indolylidene)sulfamoyl azide 101 was reduced with sodium borohydride to give a sulfamide.419 Sulfamoyl halides (F, Cl, Br, and I) have been used in the preparation of α-substituted acrylate esters which have uses in photoresist compositions and lithographic plates.413,414 2.14.5. Sulfamoyl Azides. Sulfamoyl azide, H2NSO2N3, prepared from sulfuryl chloride and sodium azide in dry ACN and sodium borohydride reacts with triphosphines PR1R2R3 (R1

3. NONCYCLIC SULFAMATE ESTERS 3.1. Structural Studies

The isothiazole 1,1-dioxide 102 reacted with sodium azide in refluxing methanol to give the sulfamate ester 103, and the X-ray structure of the latter has been determined and showed that the −SO2OMe group has cis (Z) geometry across the NC bond.420 There are several reports of crystal structures having been determined for the anticonvulsant drug topiramate 10 and other anticonvulsant compounds. X-ray, FT-IR, and FT-Raman studies

Scheme 9. Intramolecular C−H Amination with Azides Using Metalloradical Cobalt(II)

= R2 = R3 = Ph, PhO, or OEt; R1 = R2 = Ph, R3 = Cl) to give sulfamides, R1R2R3PNSO2NH2.415 A novel sulfonyl-transfer agent 2,3-dimethyl-1H-imidazolium triflate 98 with secondary amines at 0 °C generates high yields of both aromatic and aliphatic sulfamoyl azides, R1R2NSO2N3.416

have been described, and a large number of vibrational bands from the IR/Raman studies have been tentatively assigned. Thermal gravimetric analysis (TGA) and differential thermal analysis (DTA) studies from room temperature to 900 °C show that decomposition occurs in a two-step exothermal process.421 A second report determined the crystal structures of 10 and three closely related sugar sulfamates 104, 105, and 106, which are P


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almost biologically inactive.422 Topiramate has a different disposition of nitrogen and oxygen atoms from the sulfamate group with respect to the O1−S1 bond, and the nitrogen atom in topiramate is about 1 Å further away from the pyranose O6 ring oxygen than in the other three compounds. Crystal structures of the anticonvulsant esters (1,4-benzodioxin-2(3H)-yl) 107 and

(1,2,3,4-tetrahydro-2-naphthalenyl) 108 methylsulfamates have been determined, and the entities attached to the sulfamate function are in equatorial positions.423 X-ray crystal structures have been reported for the three triazaole nucleoside derivatives 109424 (R1 = CONH2,425 CSNH2,426 CN;427 R2 = NH2SO2−), which are antiparasitic agents. Their synthesis started from 109 (R1 = CONH2, CSNH2, CN; R2 = H) via cyclization with DMP in acetone and acid, sulfamation with NH2SO2Cl, treatment with NaH in THF, and finally ring opening with acetic acid to the sulfamated triazole from the sufides 116 Zefirov’s group prepared in the presence of pyridine−sulfur trioxide norbornene esters of the type 117; with norbornadiene instead of norbornene esters of type 118 are formed. 435 Similar type reactions with norbornene and pyridine−sulfur trioxide led to esters 119, and with norborna-

nucleosides.424 The same group synthesized 2-sulfamoyladenosine by four (!) different routes and established its structure using X-ray diffraction.428 The crystal structure of the 3′-N-sulfamate analog of thymidylyl(3′-5′)thymidine 110 has been determined, and a preference for the C3′-endo conformation in the solid state and in solution has been found.429 The crystal structure of oestrone 3-O-sulfamate, i.e., emate 111, which acts as an irreversible oestrone sulfatase inhibitor, was determined some years ago.430 The X-ray crystal structure of the dual aromatase−sulfatase inhibitor (DASI) 112 has been determined and helped in the design of other potent DASIs.431 The X-ray crystal structure of E2bisMATE, 113, cocrystallized with carbonic anhydrase II was interesting and showed that there was coordination between the 17-O-sulfamate group of 113 with the zinc active site and a likely additional lower affinity binding site.432

diene reaction also occurs giving esters identical to 119 but with a double bond in the 6-membered carbocyclic ring.436 Sulfenylation of tetrafluorobenzobicyclo[2.2.2]octatriene (TFBBO) with thiobis-morpholine 120 and pyridine−sulfur trioxide gave the sulfamate ester 121.437 Reaction of PhSNMe2 with norbornene and sulfamic acid gave the syn- and anti-esters 122, and an analogous reaction occurs with norbornadiene.438 With norbornene, PhSNMe2, and potassium pyrosulfate K2S2O7, which can be regarded as a complex of SO3 and K2SO4, some sulfamate 123 formed.439 An interesting extension of this work has been introduction of selenium in place of sulfur in some reactions. trans-2-Phenylselenocyclohexyl N,N-diethylsulfamate

3.2. Synthesis

3.2.1. Use of R3N−SO3, NH2SO3H, and SO3. A review by Zefirov (43 references) though titled “reactions of sulfenic acid and sulfoxylic acid derivatives with olefins in the presence of sulfur trioxide and its complexes” described work leading to synthesis of various interesting noncyclic sulfamate esters.433 Norbornene reacts with the sulfonamide p-MeC6H4SO2NMe2 in the presence of pyridine−sulfur trioxide in CH2Cl2 at −20 °C to give 38% of the sulfamate ester 114, 20% of the exo,endo ester 115, and traces of the exo,exo isomer of this ester.434 Starting Q


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Scheme 10. New, General Route to O-Substituted Sulfamates

these materials stems from their use as surfactants, and solubility and surface-active properties have been determined. 124 was made from PhSeNEt2, pyridine−sulfur trioxide, and cyclohexene in CH2Cl2 at 25 °C, and similar products can be formed using in place of cyclohexene norbornene and tetrafluorobenzobarrelene.440 Reaction of SO3 with silylamines, silazines, and silylated amides leads to formation of insertion products at one or two N− Si bonds; for example, silylamine Et 2 NSiMe 3 gives Et2NSO2OSiMe3.441 3.2.2. Miscellaneous. A new general route via orthometalation to substituted aryl O-substituted sulfamates 125 (E = CHO, CONEt2, Cl, Br, I, SnBu3, etc.) has been reported.442 Metalation at −93 °C is followed by treatment with an appropriate electrophile (E+) to give 125 in 45−96% yields (Scheme 10). In subsequent chemistry Kumada−Corriu crosscoupling some O-sulfamates with Grignard reagents gave biaryls (46−86%), and some O-sulfamates have been shown to undergo Suzuki−Miyaru cross-coupling (56−99%) generating benzynes. Poirier’s group showed that sulfamate esters loaded onto trityl chloride Ph3Cl resin can react with 1% TFA in CH2Cl2 to cleave off the sulfamate or undergo nucleophilic cleavage with 20% DEA in CH2Cl2 at 60 °C giving phenols.443 Experiments showed that this new sulfamate anchor is versatile and useful in further combinatorial solid-state synthesis of libraries. Synthesis of 17αsubstituted estradiol sulfamate and phenol libraries using as a

Novel sulfamate compounds 126 having both sulfamate and carbamate groups have been reported.448 These compounds are used for treatment of disorders of the central nervous system. Other compounds with carbamoyl and sulfamoyl functionalities incorporated in the one molecule have also been made.449 Starting from the sulfamide 127 or the sulfamate 128, the Nphosphorylsulfamide 129 and N-phosphorylsulfamate 130 have been synthesized (Scheme 12) and fully characterized. These compounds are bioisosters of pyrophosphate or carbamoylphosphate. The same researchers prepared other pyrophosphate analogs by silylating (with BrSiMe3) 130 and then hydrolyzing it to give 130 with R′ = H.450 A number of sulfamoyluridine derivatives have been prepared 131 (R1 = NH2SO2O−, (EtO)2PONHSO2O−; R2 = H, Bz).451 Sulfamate esters of benzoin, PhCH(OH)COPh 132 (R = H, Et, iPr; R′ = Me, nBu n-octyl, n-dodecyl, MeCO2−, Me(CH2)10CO−), have been synthesized. These compounds can be used to photoinitiate polymerization and cross-linking of acrylates by generating benzoyl and methylbenzoyl radicals.452 Sulfamoyl chloride has been used to synthesize derivatives of steroids to give compounds such as 20-oxo-5α-pregan-3α-yl sulfamate and the 3β-yl sulfamate, etc.376 Fourteen simple sulfamate esters RNHSO2OR′ (R = iBu, cycC6H11, 2-Me-cyc-C6H11; R′ = Me, Et, nPr, iPr, iBu, sBu, cycC6H11) were synthesized in a study of the taste of sulfamate esters. Many of these esters were found to be sweet, and thus, this work established that a negative charge on the sulfamate is not necessary for sweetness.453

Scheme 11. Two Different Synthetic Routes to Highly Fluorinated Sulfamate Esters

3.3. Reactions

solid-phase precursor 3-sulfamoyl-17α-(N-trifluoroacetyl-piperazinomethyl) estradiol was loaded onto the trityl chloride resin support and could be used to generate libraries giving yields of 18−66% with purities of 87−96%.444 Some of this work has been highlighted very briefly relatively recently by the same authors.445 Sulfamoylation starting from various functionalized alcohols and phenols has been carried out, and the method provides a means of synthesis of sulfamate peptidomimetics. Fmoc-HypRink amide resin was sulfamoylated with sulfamoyl chloride in DMA, and the product was formed in ∼95% yield.446 Excellent yields of highly fluorinated sulfamate esters F(CF2)n−(CH2)m− OSO2NH2 have been reported.447 Two synthetic routes A and B were employed for synthesis as outlined in Scheme 11. Interest in

3.3.1. Amination and Amidation. Because of the importance of C−H amination in modern synthetic organic chemistry there has been a series of reviews in this area recently. Some cover the area exclusively, and others deal with it partially in more general reviews that consider the broad area of C−H to C−X transformations. The latest progress and future directions in catalytic C−H amination have been considered in a 14 page

Scheme 12. Alternative Routes to N-Phosphorylsulfamides and -Sulfamates

review454 (∼100 references) and catalytic C−H amination: the stereoselectivity issue has been reviewed by the same group (70 references) very recently.455 Selective functionalization of R


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saturated C−H bonds with metal porphyrin catalysts has been reviewed in 25 pages with ≥250 references.456 Part of a review on seven-membered rings is also useful.457 Du Bois reviewed (152 references) metal-catalyzed oxidations of C−H to C−N bonds (∼80 references),458 and very recently a short review (∼80 references) on rhodium-catalyzed C−H amination appeared.459 Scheme 13. Intermolecular Amination of Allyl Alcohols and Sulfamates

amination during Rh-catalyzed sulfamate ester cyclization has been reported.472 Use of ruthenium(II)pyridine bis-oxazoline (pybox) catalyst, e.g., 137, resulted in very successful enantioselective intramolecular C−H aminations of sulfamate esters.473 The tethered carboxylate Rh2(esp)2 catalyst with PhI(O2CtBu)2 catalyzed allene amination in sulfamate esters like NH2SO2O(CH2)2C(R)CCH2, giving aminocyclopropane products with up to 82% ee and 53% yield.474 These authors very recently highlighted the reactivity patterns for the very versatile 2-amidoallylcation involved in these reactions as an intermediate.475 A stereospecific synthesis of 1,N2-deoxyguanosine adducts has been developed starting from an enantiomerically pure sulfamate and using Rh2(OAc)2, MgO, and Ph(OAc)2 as a catalyst set.476

Intramolecular metal-catalyzed amination of a pseudoanomeric bond in a C−H glycoside using Rh2(OAc)4, PhI(OAc)2, and Scheme 14. Oxidative C−H Amination of Chiral Sulfamate Esters

MgO with β-C-sulfamoyloxymethyl glycoside 133 gave 134 and 135.460 The same workers used a similar catalytic system to effect amination in an azacycloalkane system.461 Intramolecular C−H amination starting from azides in the presence of metalloradical cobalt(II) complexes of porphyrins leading to 1,3-diamines (see Scheme 9) has been described earlier.417 Using the same catalyst these researchers obtained chemoselective intramolecular allylic C−H amination of both Nbis-homoallylic and N-allylic sulfamoyl azides leading to allylic 1,3-diamines.462 A mercury catalyst Hg(OTf)2 has been used to obtain intermolecular amination of allyl alcohols with sulfamates (Scheme 13).463 Du Bois and his group made major contributions to C−H amination reactions involving sulfamate esters. In Scheme 14 a typical example is shown using Rh2(OAc)2, MgO, and Ph(OAc)2 as a catalyst set; here the sulfamate ester undergoes selective intramolecular cyclization leading to diamines or other 1,3disubstituted products.464 They showed that oxidative C−H amination of chiral sulfamate esters takes place very well with excellent diastereocontrol using the same catalyst set.465 Benzo-fused cyclic sulfamates have been prepared using this methodology starting from ortho-substituted phenols. The heterocycles thus formed can undergo Ni-catalyzed crosscoupling with Grignard reagents.466 N-Trichloroethoxysulfonyl-protected ureas and guanidines undergo C−H amination with good yields in the presence of a tethered carboxylate catalyst Rh2(esp)2 together with the other two components of the catalytic set used above.467 Catalytic intermolecular amination of C−H bonds has also been probed,468 and sequential Pd and Rh catalysts have been employed in asymmetric synthesis of diamine derivatives.469 A strategy for preparation of aconitine, a poisonous compound from the perennial Aconitum genus, has been developed using C−H amination.470 Various rhodium catalysts have been examined in order to maximize product yields and % ee in enantioselective C−H amination, and the most successful was a rhodium dimer referred to as 136 which could ring close allylic C−H bonds in sulfamate esters in ∼50% yields with % ee up to 84%.471 A rare example of inverted regioselectivity in C−H

Intramolecular amidation of aromatic sulfamates NH2SO2OC6H3R-o,X-p with MgO and PhI(OAc)2 and chiral Rh(II) catalyst (R1 = tBu) Rh2[(S)-nttl]4 or Rh2[(R)-ntv]4 (R1 = iPr) 138 gives 139 in moderate yield after trapping of the intermediate nitrene by insertion into the C−H bond.477 Intermolecular amidation of Indane with an arylsulfamate NH2SO2OAr gave 1-ArOSO2NH-Indane.477 The same research group also reported a “first” in obtaining the intramolecular asymmetric amidation of sulphonamides R(CH2)4SO2NH2 (R = H, Me, Et, and CH2CH) with the same catalysts.478 Enantioselective intramolecular C−H amidation of Indane-2 sulfamate was achieved with a similar catalytic set but using Rh2(S-TFPTTL)4 140 as the dirhodium catalyst giving 37−98% yields of 141 with % ee of 18−48.479 The Che group added to our knowledge of C−H intramolecular amidation with a series of papers over the last 10 years or so. Ruthenium porphyrin catalysts such as 142 with PhI(OAc)2 successfully synthesized cyclic sulfamate esters in yields of 39−77% and % ee up to 87%.480 A mechanism involving a reactive imido ruthenium porphyrin intermediate was S


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MgO to give as products 145 in good yields with % ee up to 80.477 Aziridination of 4-octene using RCH2OSO2NH2 (R = Cl3C, Me) and p-trifluorodiacetoxybromobenzene, p-F3CC6H4Br-

(AcO)2, gave good yields of 146 with varying cis/trans ratios.490 Aziridination of glycals with Rh2(OAc)2, MgO, and Ph(OAc)2 provides a simple method for stereoselective synthesis of polyfunctionalized α- or β-aminosaccharides.491 Several groups have used copper complexes as catalysts to effect aziridination. Aliphatic alkenes react with Cl3CCH2OSO2NH2 in chlorobenzene at 25 °C in the presence of IPrCu(dibenzoylmethane) giving the aziridine 147.492 Copper iodide-catalyzed aziridination of p-RC6H4CHCH2 with the same sulfamate ester gave yields of 148 varying from 41% to 68% for five different R’s.493 Copper catalysts to effect aziridination have been extensively used by the Dodd and Dauben group. Iodosylbenzene, PhIO, and Cu(MeCN)4PF6 have been used with sulfamates such as NH2SO2O(CH2)3CH CH2 and gave good yields of product 149.494 The bicyclic fused aziridines formed could be opened with nucleophiles to give the corresponding substituted cyclic sulfamates. This methodology has been put to use by the same group to prepare a rigid analogue of allopregnanolone having a sulfamoyl aziridine group on the β face at the C5−C6 position.495 Intramolecular copper-catalyzed aziridination with Cu-

proposed. The mechanism involved in these reactions has been looked at (see section 3.4 below).480,481 Disilver(I) with various pyridine ligands and PhI(OAc)2 in ACN at 82 °C gave yields of up to 90% sulfamate ester by intramolecular amidation.482 Chiral Scheme 15. Aziridination of Alkenes with Trichloroethoxysulfonyl Azide

magnesium(III) Schiff-base complexes were also used to achieve intramolecular amidation of sulfamate esters to give up to 90% yield under mild conditions.483 Scheme 16. Diastereoselective Alkene Aziridination Using Rhodium and Magnesium Catalysts

3.3.2. Aziridination. A review on “recent developments in asymmetric aziridination” has appeared (>200 references),484 and a short book chapter on preparing aziridines has some references on the use of sulfamates in this context.485 A short “edge article” on allylic C−H amination versus CC aziridination through Co(II)-based metalloradical catalysis has been recently published.462 Chiral Co(II)−porphyrin-catalyzed aziridination of alkenes with trichloroethoxysulfonyl azide gave the corresponding aziridines in 93% yield and % ee up to 99. A typical reaction is shown in Scheme 15.486 Du Bois demonstrated that diastereoselective alkene aziridination occurs in ∼90% product yield using Rh2(OAc)2, MgO, and Ph(OAc)2 as a catalyst set. An example of this is given in Scheme 16.465 They prepared excellent yields of aziridines 143 starting from R1R2CCHCH2R3 and Cl3CCH2OSO2NH2 and using the same set of catalysts but replacing the rhodium catalyst with Rh2(CF3CONH)4.487 Use of this catalyst was extended later to effect the synthesis of unique alkoxysulfonyl aziridine heterocycles through both intra- and intermolecular olefin aziridination.488 A novel group of bicyclic aziridines made from rhodiumcatalyzed reaction of allylic hydroxylamine-derived sulfamates has been reported.489 2-Allyl-substituted sulfamates 144 failed to undergo insertion but did react exclusively to give intramolecular aziridination with rhodium(II) catalysts and PhI(OAc)2 and

(MeCN)4PF6 and the bis-1,3-oxazole ligand 150 in ACN with NH2SO2O(CH2)2CHCHPh gave 86% yield with % ee = 84. Compounds such as 150 undergo SN2-type attack by benzylamine and p-bromobenzyl alcohol resulting in ring opening and leading to a variety of other cyclic sulfamates.496 These SN2 ringopening reactions have very recently been studied per se using Grignard reagents, lithium salts of terminal alkynes, dithiane, malonate, and high levels of regio- and chemoselectivity to give cyclic sulfamates in good yields.497 Copper-catalyzed aminoacetooxylation of some cyclic sulfamates has been effected in good yields using Cu(MeCN)4PF6 and Ph(OAc)2.498 Aminohydroxylation using homoallylic sulfamate esters gives cyclic sulfamate esters 151 in about 60% yield on reacting NH2SO2O(CH2)2CHCH2 in aqueous nPrOH and NaOH.499 3.3.3. Other Reactions. Under solid−liquid phase transfer conditions 2-fluoro-2-phenylethyl p-toluenesulfonate, PhCHFCH 2 OSO 2 C 6 H 4 Me-p, reacted with sulfamates NH2SO2OR to give β-fluoroethers PhCHFCH2OR, but if 2,4,6-trimethylphenylsulfamate was used as substrate the N,Ndisubstituted sulfamate (PhCHFCH2)2NSO2OC6H3Me3 was formed.500 In a later paper from the same group a series of aliphatic and aromatic sulfamates were reacted with pfluorobenzyl bromide, giving again disubstituted sulfamates T


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a n d et h e r s . 5 0 1 P h en y l [ O ] b e t y l a t e fl u o r o s u lf a t e , Me3N+SO2OPhFSO3−, the first example of a [O]betylate

min with nickel catalysts improved Suzuki−Miyaura coupling reactions between arylsulfamates and boronic acids 156 in terms of reaction time, reduction in catalyst, and boronic acid stoichiometry and allowed scale up.511 3.4. Mechanistic Studies

Du Bois’s group recently used the new catalyst Ru2(hp)4Cl to effect intramolecular allylic C−H amination with bis-homoallylic sulfamates (Scheme 17).512 Their computational and experimental studies support a mechanism for the amination involving H-bond abstraction and radical recombination with a short-lived diradical species. Che’s group carried out a DFT computational study of the catalytic pathway of the ruthenium−porphyrincatalyzed intramolecular amidation of sulfamates which includes a crucial metal−nitrene reactive intermediate.481 In previous work they supported the involvement of a reactive imido ruthenium porphyrin intermediate in these reactions.480 The mechanism of the rhodium-catalyzed aziridination of sulfamate glycals (and their ring opening with nucleophiles) involving nitrenes was studied using DFT with inclusion of solvent effects in the calculations. Initially the reaction involves a triplet ground state and subsequent intersystem crossing to a singlet.513 Suzuki−Miyaura cross-coupling reactions with sulfamate esters have also been the subject of DFT calculations, and the full catalytic cycles for these reactions have been arrived at. The oxidative addition step involves a five-centered TS.508 Work by Williams46 on structure/reactivity and structure/structure correlations for sulfate monoester salts ROSO3K and sulfamate esters ROSO 2 NH 2 has shown that the mechanism of nucleophilic reaction of both involves substantial S−O bond lengthening and a dissociative sulfur trioxide-like TS. In an important extension of this work they studied the inactivation of Pseudomonas aeruginosa arylsulfatase by a series of arylsulfamates including the medicinally important compounds, coumate, 667coumate (STX64), and flavomate, and they found that inactivation was time dependent, irreversible, and active-site directed. A Bronsted plot (for nine sulfamates with r2 = 0.85) of kinact/Ki (Ki is the inhibition constant for phenyl sulfamate) gave βlg = −1.1, which indicates that there is a large amount of charge transfer and extensive cleavage of the ArO−S bond in the TS.514 Using 3-nitrophenylsulfamate the kinetics of inactivation of a number of sulfatases have been determined, and arylsulfamates are seen as being broad spectrum inactivators of sulfatases and having great potential for further use.515 This group also reported a detailed computational and crystallographic study of the sulfonyl and phosphonyl groups including the sulfamate moiety.516 Studies on the kinetics of hydrolysis and aminolysis of sulfamate esters have provided useful insights into the mechanisms occurring. Hydrolysis/aminolysis of esters RNHSO2ONp in aqueous EtOH and aqueous ACN in the presence of excess amine showed that there were competitive reactions between hydrolysis leading to formation of sulfamate salts, RNHSO2O−R′NH3+, and aminolysis giving sulfamide, RNHSO2NHR′, products. Hydrolysis with a lower activation energy was favored, and even in the presence of 1 mol·dm−1 amine the ratio of sulfamate to sulfamide formed was 1:1. A Hammett ρ of −1.8 in conjunction with other data suggested that not only was the S···ONp bond stretched but also that bond making of an N−S bond in an incipient N-sulfonylamines, RN SO2, was well advanced.363 In aminolysis of sulfamate esters in nonaqueous solvents evidence consistent with an E2-type mechanism with some E1cB-like character was found.362 N-

(trialkylammoniosulfate ester), was prepared by reaction of methyl fluorosulfate MeOSO2F on phenyl-N,N-dimethylsulfamate, Me2NSO2OPh.502 The 2,2,2-trichloroethyl group, introduced as the trichloroethyl ester of chlorosulfonic acid, ClSO2OCH2CCl3, can act as a protecting group for the sulfamoyl function during glycosylation. It can be removed with zinc and ammonium chloride (in MeOH at room temperature) but survived a variety of other experimental procedures.503 A sequence of reactions starting from 3-phenylpropanol to Ph(CH2)3OSO2NH2 and cyclization to 152 leads to the serotin inhibitor dapoxetine 153.504 Starting with ethyl (S)-lactate ethyl(R)-2-(trifluoromethylsulfonyloxy)propanoate 154 has been made in a series of steps involving N-methylsulfamoyl chloride, dimethylsulfate, and trifluorosulfonic acid.505 There has been interest in cross-coupling reactions involving sulfamates. Starting from the sulfamate XC6H4OSO2NEt2 and Grignard reagents biaryls XC6H4−Ar have been made using a nickel catalyst (see section 3.2.2).442 A review on nickel-catalyzed cross-couplings involving carbon−oxygen bonds has appeared very recently, and a small section of this is devoted to crosscoupling of aryl sulfamates leading to biaryls.506 Nickel-catalyzed Suzuki−Miyaura cross-coupling with arylboronic acids, pXC6H4B(OH)2, and a large number of arylsulfamates gave biaryls Ar−Ar in excellent yields and much better than when aryl carbamates or carbonates were employed.507 The nickel complex

NiCl2(Pcyc-C6H11)3 was used for these reactions. Other examples of this reaction have been published more recently by the same group, and DFT calculations have provided details of the catalytic cycles for the Suzuki−Miyaura cross-coupling.508 Scheme 17. Intramolecular Allylic C−H Amination with BisHomoallylic Sulfamates

They showed how cross-coupling reactions with morpholine or other secondary amines and arylsulfamates can be carried out very successfully with Ni(cyclooctadiene)2 and sodium tertbutoxide leading to Ar−NC4H8O when morpholine was used.509 Ni(cyclooctadiene)2, PCy3, and arylsulfamates with boronates 155 were used to extend the scope of these cross-coupling reactions considerably.510 Microwave heating at 180 °C for 10 U


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Scheme 20. Acid-Catalyzed Reaction Pathway of NAcylsulfamates

Sulfonylamines were not thought to be involved. Under certain conditions nonlinear kinetics were observed during aminolysis of sulfamate esters in CHCl3, and these were interpreted in terms of formation of a substrate (S) amine complex, [S·Amine], whose breakup was rate determining.517 Use of βnuc values to help assign various elimination mechanisms for sulfamate esters has been discussed.518 A change in the rate-determining step in an E1cB mechanism during aminolysis of sulfamate esters in ACN was detected in an unusual way as a result of differences in entropy values and Bronsted plots.519,520 Using structure− and solvent−reactivity studies, thermodynamic data, a “nucleophilicity test”, and KSIE of arylsulfamate esters, p-XC6H4OSO2NH2, it is proposed that the mechanism of their hydrolysis at pH = 2 involves the neutral ester undergoing nucleophilic attack by water in a bimolecular TS.521 Many sulfamate esters can be looked on as models for those that are biologically important, and thus, the study of their aminolysis is relevant to an understanding of the mechanism of action in blocking enzymatic processes. Analysis of Bronsted plots both

where comparison is possible they are better than those reported in the literature. 3.5. N-Acylsulfamates

More than 25 papers that involve the N-acylsulfamate moiety, −OSO2NH(CO)−, have appeared over the time span of this

Scheme 18. Thia−Fries Rearrangement of Phenylsulfamate Esters

review. Synthesis a series of sulfamates of type 157 (R = substituted aryl and CCl3CH2 and R1 = C6H5, nPr, and Me(CH2)9CH2) were achieved in good yields using Grignard reagents in aqueous ether (Scheme 19).526 The mechanism of the acid-catalyzed hydrolysis of the sulfamates 158 according to the pathway shown in Scheme 20 involves water in the transition state as shown in 159. These N-acylsulfamate esters are models for more complex biologically important esters.527 Series of N,Ndiacylsulfamates 160 have been prepared in good yields by reaction of ROSO2NCO isocyanates, this time with dicarboxylic acids in toluene and Et3N at 20 °C.528 One of the most important N-acylsulfamates is Avasimibe 161, which is a selective ACAT inhibitory lipid-regulating agent, and many aspects have been succinctly reviewed by Burnett and Huff529 including synthesis and structure−activity relationships, pharmacology, toxicity, metabolism, and its clinical development in which it reached phase III in trials. A pilot-scale process for synthesis of 161 starting from 2,4,6triisopropylbenzyl chloride 162 has been described.530 Avasimibe has been shown to act synergistically with atorvastatin, better known as Lipitor, to reduce cholesteryl ester content in THP-1 cells.531 Synthesis of the N-acylsulfamates 163,532 which is an analog of β-aspartyl-AMP, and isoleucyl (R = IIe) and methionyl (R = Met) sulfamate adenylates 164533 have been reported. Sulfamoylation of an 8-oxoadenosine derivative with sulfamoyl chloride gave the new phosmidosine analog 165 in which the proline and 8-oxoadenosine moieties are linked via an Nacylsulfamate bridge.534 Cysteinyl transferase mycothiol ligase, MshC, is selectively inhibited by the acylsulfamate cysteinyl sulfamoyl adenosine 166.535 A large number of 5′-O-(N-dipeptidyl)-sulfamoyladenosines 167 have been prepared. Changing R1 and R2 allows variation of the amino acids at the amino (R1) and the carboxyl (R2) terminals of 167.536 Pantothenate synthetase catalyzes the ATP-dependent condensation of D-pantoate and β-alanine to form pantothenate, and a series of sulfamoyl analogs 168 (R = tBuCO−, MeO-

“normal” rectilinear and biphasic for the reactions of amines with sulfamate esters has helped to elucidate the elimination mechanisms taking place, and both E2 and E1cB types have been supported from analysis of Leffler indices. These reactions are seen as involving N-sulfonylamines, NHSO2.522,523 Lastly, the kinetics of hydrolysis of emate 111, one of the most important sulfamate enzymatic inhibitors, has been studied under physiological and higher pH conditions. Analysis of pH/ H−−rate profiles, solvent−reactivity, KSIEs, and activation data show that an SN2 solvolytic mechanism is followed in the pH range from ∼1 to ∼8, and above the pKa of emate (∼9) a second decomposition route is followed which shows a first-order dependence on base; here, an E1cB mechanism is supported.524 A thia−Fries rearrangement of phenylsulfamate esters in AlCl3 gives good yields of p- and o-arylhydroxysulfonamides, Scheme 18.525 The higher ortho/para ratios (≥1 and as high as 2.7) found Scheme 19. Synthesis of N-Acylsulfamates from Sulfonylisocyanates and Grignard Reagents

at lower temperatures (90−110 °C) and shorter reaction times (5−30 min) may indicate an intramolecular mechanism for this new rearrangement. Experiments showed that the para isomer does not rearrange to the ortho isomer under rearrangement conditions. At higher temperatures the ortho/para ratio is ∼0.5 and the para isomer probably forms by a different route than the ortho one. Yields of arylhydroxysulfonamides are good, and

V


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the potential of nucleoside inhibitors based on 5′-O-[N(salicyl)sulfamoyl]adenosine (Sal-AMS), 170 (R = OH, X = Na and R = H, X = H), as novel antibiotics targeting siderophore biosynthesis and covering synthesis, physiochemical properties, metabolism, and biological activity, etc., appeared covering the literature into 2006.539 A structure−activity study of new derivatives indicates the importance of the aryl ring and the positioning of substituents. Substitution of ring carbons with nitrogen and oxygen atoms effects the potency of these inhibitors greatly. SAR studies of the glycosyl domain 540 of the Scheme 21. Outline of the General Strategy for Synthesis of the Arylsulfamoyl-Containing Macrocycles 176

(CH2)2CH(OH)−, MeOCH2CMe2C(OH)−, tBuC(OH)−, and tBuC(NH3+)−) of the reaction intermediate pantoyl adenylate has been synthesized.537 These sulfamoyl derivatives proved to be more potent inhibitors than several ester analogues. The acylsulfamate analog 169 of luciferyl-AMP is a stable and potent analog of firefly luciferase.538 Some years ago a review on

acylsulfamate linker and the purine have been reported.541 A number of 2-triazole-substituted derivatives of 170 have also been examined.542 An extensive structure−activity study of the

inhibition of the bifunctional enzyme salicyl-AMP ligase (MbtA) by 170 has been reported using a large number of analogs of 170.543−545 A fluorescent probe 171546 based on 170 and a d4labeled Sal-AMS 172547 has been synthesized for assay purposes. Compound 171 has been used in a high-throughput screening to identify a new inhibitor of the self-standing adenylation enzyme BasE.548 Both 170 and its analog 5′-O-[N-(2,3dihydroxybenzoyl)sulfamoyl]adenosine, DHB-AMS, 173, are slow-onset tight-binding inhibitors of the enzyme EntE, which catalyzes the ATP-dependent condensation of 2,3-dihydroxybenzoic acid and phosphopantetheinylated EntB to form covalently arylated EntB.549 In Scheme 21 starting from 174 via 175 the acylsulfamoylcontaining macrocycles 176 have been synthesized, and 176 with X = L−NH2 were potent inhibitors in a cysteine adenylation assay.550 Compound 177, which is a bisubstrate inhibitor of MtBPL, has been described and evaluated recently.551 W


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3.6. N-Sulfonate Carbamates

Series of diesters of sulfamic/carbamic acids have been prepared by reaction of chlorosulfonylisocyanate and various phenols giving the sulfamoyl chlorides, R1OCO2NHSO2Cl, which on further reaction with phenols, R2OH, give the N-sulfonate carbamates, R1OCO2NHSO2OR2 (R1 = Ph, and a range of substituted phenyls, 1- and 2-naphthyls; R2 = 2,4,6-trichloro-, pentachloro-, and 2,6-dibromo-4-cyanophenyls), in generally good to excellent yields. These compounds have broad spectrum fungicidal activity. At higher temperatures reaction of chlor-

osulfonylisocyanate with phenols produces ROSO2NCO, which hydrolyzes to the sulfonated carbamic acid ROSO2NHCO2H and eventually gives the sulfamate ester ROSO2NH2.552 The kinetics and mechanism of hydrolysis of compounds 178 have been studied over the full pH range at 50 °C. These compounds can undergo both S−O and C−O cleavage, and in acidic conditions both occur. It was found that a C−O cleavage reaction involving protonation of leaving MeOH and its expulsion from the zwitterion, ArOSO2N−COOH+Me, occurs and that S−O cleavage involving either intra- or intermolecular acid-catalyzed breakup of 178 or its zwitterion also takes place.553 This study was followed by that of the related compound N(phenoxy)-carbonylsulfamate 179 under similar conditions. The mechanisms involve the anionic form of 179 and C−O bond cleavage.554 N-(Substituted phenoxycarbonyl)sulfamates 180 were studied later, and two competitive hydrolysis reactions were found to be taking place: a general acid-catalyzed acyl-oxygen cleavage of the anions of 180 and a methyl-oxygen cleavage from water attack on 180.555 When ascomycin was treated with chlorosulfonylisocyanate followed by reaction with MeOH the immunosuppressant 181 was formed. 556 Treatment of rapamycin with methyl(carboxysulfamoyl)triethylammonium gave the immunosuppressant 182.557 New types of membrane-associated UDPglycosyltransferase inhibitors which link a 2-decanoylamino-3phenylpropyl moiety with uridine in 183 (R = H, OH) through various spacers (X) including −CH2OCONHSO2O− have been prepared.558 Reaction of chlorosulfonylisocyanate with 2′,3′isopropylideneuridine and 2,3,4,6-tetra-O-benzyl-α-D-glucopyranose gave 184, which inhibited glycosylation of proteins in HSV-1-infected HeLa cells. Various other derivatives were made including one in which the direction of the spacer moiety in 184 is reversed, i.e., the carbamoyl group is attached to the uridine unit.559 A new water-soluble acyl-CoA:cholesterol O-acyl transferase (ACAT) inhibitor 185 has been made from reaction of chlorosulfonylisocyanate with 2,6-diisopropylphenol in THF at 0 °C.560 Other similar derivatives where the spacer between the two rings is changed to −OSO2NHCOCH2− and one of the rings carrying an extra isopropyl group have also been made.561 The same group also prepared other different types of ACAT inhibitors, such as the N-sulfonated ureas, R1R2NCONR3SO2OR4, and the N-sulfonated carbamates (X = O) and thiocarbamates (X = S), ArXCONR1SO2OR2. Various compounds in the series showed different potencies, and structure−activity relationships (SARs) have been established.562

4. CYCLIC SULFAMATE ESTERS 4.1. Structural Studies

The first structural study of a cyclic sulfamate methyl DL-3benzyl-2,2-dioxo-1,2,3-oxathiazolidine-4-carboxylate 186 was reported almost 20 years ago. The bonding at the nitrogen atom shows almost planar geometry with the sum of the angles being 357.8°.563 Structures of 187 (R = Boc, 4-FC6H4−) have X


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synthesis of 4,5-diaryl cyclic sulfamates under similar conditions with yields of 99% and % ee about the same.571 Using very similar

been examined using NMR, X-ray diffraction, and DFT calculations, and twisted boat and chair conformations, respectively, were observed. These are the first 6-membered cyclic sulfamates that have had their structures determined.564 The crystal structure of the closely related compound 188 has been reported more recently.565 This compound made from sulfamoyl chloride and 3-phenyl-1-propanol is an intermediate on the route to selective serotin reuptake inhibitor (SSI) dapoxetine.

Scheme 23. Synthesis of Chiral Cyclic Sulfamates from βAminoalcohols Using Thionyl Chloride

conditions another group also achieved excellent enantioselective synthesis of cyclic sulfamates and prepared the precursor Nsulfonylamines in fair yields by reaction of 2-hydroxyacetophenone with sulfamate esters, NH2SO2OR.572 The platinum catalyst [Cl2Pt(CH2CH2)2] in THF at room temperature successfully cyclizes the propargylic acetate sulfamate esters NH2SO2O(R2)CCH2C(OAc)C−CCR1 to give the cyclic sulfamates 192 with a cis:trans ratio of ∼22:1.573

Scheme 22. Enantioselective Synthesis of Cyclosulfamates

Scheme 24. Use of the Burgess Reagent with Epoxides To Synthesize Cyclic Sulfamates

Addition of Grignard reagents RMgBr (R = Me, Et, iPr, allyl, vinyl, Ph, PhCC, and (CH2)2C4H7O2) to sulfonylimines, such as 191 with R2 = H, presents an easy method for making cyclic sulfamates 193 in moderate yields.574

4.2. Synthesis

Two reviews highlighted much of the chemistry involved with cyclic sulfamates. The first one titled “synthesis and reactivity of cyclic sulfamidities and sulfamidates” appeared in 2003, has over 60 relevant references, and covers the area very well up to that time.566 The second review is very recent, has an emphasis on cyclic sulfites, sulfates, and sulfamidates in carbohydrate chemistry, and has about 15 pertinent references to cyclic sulfamates.567

Electrocatalytic oxidation of cyclic sulfamates in a solvent system containing active metal and a nonmetal oxidant (RuO4) gave the oxathiazololine 189.568 An efficient enantioselective synthesis (with up to 99% ee) of cyclic sulfamates with yields of >90% has been discovered via asymmetric hydrogenation with the palladium catalyst, Pd(CF3CO2)2, with (S,S)-f-binaphane 190 of the corresponding cyclic N-sulfonylimines at room temperature in TFE for 12 h (Scheme 22).569 Hydrogenation of N-sulfonylimines 191 with a chiral rhodium catalyst either (S,S)- or (R,R)-2,Cp*RhCl(TsDPEN) using formic acid/Et3N as a hydrogen source gave >90% yields and generally excellent % ee at room temperature in 0.5 h.570 The same group has dynamic kinetic resolution in the stereoselective

The N-2-pyridyl cyclic sulfamates 194 can be made from Ph2CHNH2 and 195 in ACN at room temperature under argon gas for 2 days, giving ∼80%.575 Chiral cyclic sulfamates were synthesized from β-aminoalcohols with thionyl chloride and Et3N followed by RuO4 oxidation (Scheme 23). They were then used in fluorination reactions with TBAF, giving rise to useful chiral N-benzylfluoroamines.576 The same group found a useful route to N-alkyl cyclic sulfamates starting from Boc-protected β-aminoalcohols which were converted to cyclic sulfamates and deprotected with TFA, and the resulting cyclic sulfamates were reacted with benzyl Y


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bromide and BnBu 3 NCl. 5 7 7 The Burgess reagent, (methoxycarbonylsulfamoyl)triethylammonium hydroxide, 196, has been used with epoxides to synthesize cyclic sulfamates (Scheme 24).578 It is of interest that with aromatic epoxides a ring enlargement takes place, and thus, with styrene oxide 197 forms; its structure was unequivocally established by X-ray. The Burgess reagent has again found use in stereoselective synthesis of α- and β-glycosylamines incorporating a cyclic sulfamate moiety.579 A Russian group made 1,5,2,6,3,7-dioxadithiadiazocine tetroxides 198 (R = Et2N, (CH2)5N, and O(CH2)4N) starting from the appropriate N-cyanoamide, RCN, and reacting with SO3 in CH2Cl2 at −80 °C with yields varying from 27% to 42%.580 The same group using SO3 in ether and the same cyanamides and in addition those with R = Me2N and 1pyrrolidinyl synthesized the six-membered oxathiadiazine rings 199.581 Both Baker’s yeast and lipase-catalyzed cyclization have been used to prepare 1,3-benzoxazine-2,4-diones 200, X = CO, 4-oxo3,4-dihydro-1,2,3-benzoxathiazine 2,2-dioxides 200, X = SO2 and

Methoxybenzyl)-2-amino-3-benzyl-3-propanol 204 was converted into its cyclic sulfamate 1,2,3-oxathiazolidine S,S-dioxide 205 by reaction with SOCl2, and it in turn can undergo nucleophilic attack to give a β-fluoroamine (with F−), a β-

azidoamine (with N3−), or a β-cyanoamine (with CN−) 206 (X = F, N3, and CN).586 Five- and six-membered cyclic sulfamates such as 207 and 208 ring opened on nucleophilic attack by various nucleophiles to give compounds of general type BnNHC(R1)(R2)−CH(R3)(R4), where R4 = N3, CN, F, NH(CH2)3CH3.587 The cyclic sulfamate 209 of (S)-prolinol 210 was obtained by reaction of sulfuryl chloride, Et3N in chloroform at −78 °C, and subsequent oxidation to give 209.588 Compound 209 undergoes nucleophilic (R2NH, MeOH) ring opening. Nucleophilic ring opening of the cyclic sulfamate derived from (S)-serine 211 gave β-substituted alanines, NucCH2CH(CO2tBu)NHBn.589 Cyclic sulfamates 212 (R = OMe, N(OMe)Me), synthesized using the Burgess reagent on reacting with nucleophiles can undergo both SN2 and E2 reactions, but careful choice of the conditions can favor one or the other. The reactions provide a facile method of making β2,2amino acids.590,591 Reaction of the diol 213 with the Burgess reagent on refluxing in THF gave the cyclic sulfamate 214, and with aqueous HCl the ring opens to give the new α,α-disubstituted β-amino acid, (S)-αtrifluoromethylisoserine 215.592

Stereoselective synthesis of new bis-amino acids (S,R)- and (R,R)-α-methylnorlanthiones has been achieved by SN2 attack on a cyclic sulfamate by the SH of a protected cysteine.593 Again, SH attack of a thiosugar on the same cyclic sulfamate gave rise to the sugar amino acid hybrids S-glycosyl-α-methylisocysteines.594 Synthesis of two more new α,α-disubstituted β-amino acids 216 (R = H, Ph) was achieved by ring opening of an αmethylisoserine cyclic sulfamate with sulfur nucleophiles.595 Using O-nucleophiles with the cyclic sulfamates 217 (R = N(OMe)Me, OMe) inversion of configuration occurs at the quaternary center, which allows stereoselective synthesis of β2,2-amino acids 218.596 In a recent paper these authors used the chiral sulfamates 217 and imidazoles and pyrazoles as nucleophiles to ring open 217 with inversion of configuration at the quaternary carbon retaining the enantiomeric excess of the substrate. This reaction paves the way to several important amino acid derivatives.597 A number of unnatural α,α-disubstituted amino acid derivatives have been prepared by nucleophilic attack (azide, cyanide, thiocyanate, piperidine, 4-MeOC6H4CH2S−H (and S−Li), etc.) on the cyclic sulfamate 219.598

4-phenyl-1,3-benzoxazin-2-ones 201.582 The same researchers using ultrasound and Baker’s yeast prepared the heterocycles 202 with X = O, NH, NMe, and NPh; Y = CO and X = O; Y = SO2 by cyclization of suitable benzonitriles.583 Synthesis of three bicyclic sulfamates 203 (with n,m = 1,2, 2,1, and 2,2) made from (S)-prolinol and 2(RS)-piperidine-methanol reacting with thionyl chloride has been achieved, and their configurations have been established.584 Synthesis of myo-inositol 1,4,5-trisulfamate, an isosteric analog of myo-inositol, using sulfamoyl chloride and sodium hydride in DMF has been reported.585 4.3. Reactions

4.3.1. Nucleophilic. A very large number of reactions have as their central theme nucleophilic attack at cyclic sulfamates. N-(p-

Z


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intermediates in the synthesis of the biologically important compounds (−)-paroxetine (antidepressant) and (+)-laccarin

using C(3)-substituted 1,2-cyclic sulfamates with C-nucleophiles.609 The important late precursor (3S)-3-methyl-1,4benzoxazine of the drug levofloxacin can be made with regiospecificity by nucleophilic cleavage of type 227 compounds using the sodium salts of various bromophenols, thiobromophenols, and bromoanilines as nucleophiles.610 Further reaction of compound 227 with enolates R1O(C O)CH2R2 (R1 = Me, R2 = SPh, S(O)Ph, SO2Ph; R1 = Et, R2 = S(O)Me) giving 5- and 6-substituted α-phenylthio lactams providing an entry to α,β-unsaturated lactams has been explored.611 Five 1,2- and 1,3-cyclic sulfamates have been reacted with the enolates EtO2CCH2P(O)(OR)2 with R = Et, iPr and gave fiveand six-ring α-phosphono lactams.612 These reactions of 1,2- and 1,3-sulfamates with enolates have been exploited further using dienolates 231 to generate substituted enantiopure alkylidenated pyrrolidines and piperidines.613 Phenol, N-substituted aniline, and thiophenol nucleophiles 232 (X = O, S, and TsN) cleave enantiomerically to pure 1,2-cyclic sulfamates, and the products after undergoing Mitsunobu reactions give substituted 1,4tetrahydrobenzoxazepines, benzothiazepines, and benzodiazepines.614 This chemistry has been reviewed fairly recently by these researchers under the title “N-heterocycle construction via cyclic sulfamidates applications to synthesis” in a perspective article containing ∼170 references.615 Cyclic sulfamates derived from serine have played an important role in synthesis. The cyclic sulfamate derived from N-trityl-L-serine ethyl ester 233 has been prepared in three steps

Nucleophilic displacement at C-3 from the D-allosaminederived cyclic sulfamate 220 occurred with thionucleophiles and azide ion but with N and O nucleophiles elimination, and deacetylation also occurred.599 A route to 3-thioglucosamine derivatives leading to thiooligosaccharides is discussed.600 Synthesis of the trisaccharide 221 was achieved in 77% yield using a ring-opening reaction of an appropriate precursor cyclic

sulfamate.601 Nucleophilic ring opening of the cyclic sulfamate 222 was crucial in providing a route to stereochemically pure derivatives of the amino acids meso-lanthione and β-methyllanthionine precursors to lantibiotic analogues.602 Amine (NHR1R2) ring opening in ACN of cyclic sulfamate 223 gave the β-aminosulfamic acids BnN(SO3−)CH(CO2Et)CH2NHR1R2, which on further reaction gave 2,3-diaminopropanoate derivatives.603 A number of orthogonally protected sulfamates such as 224 were prepared by reaction of Burgess-type reagents with diols such as p-MeOC6H4CHOHCH2OH in up 91% yield.604

A useful route to N-heterocycles has been reported by the Gallagher group using 225 in base with methyl thioglycolate MeO2C−(CH2)2XH with X = S and various α-amino esters with X = NR3 giving nucleophilic displacement and leading via lactamization to series of either thiomorpholine or piperazine derivatives 226 depending on the choice of nucleophile.605 Their studies have been extended to include the 1,2- and 1,3-sulfamates 227, n = 1,2, which can react with stabilized enolates EtO2CCHX (X = CO2Et, P(O)(OEt)2, etc.), giving via lactamization substituted α-functionalized pyrrolidone and piperidinone derivatives.606 They applied their lactam methodology to synthesis of the natural product (−)-aphanorphine 228 isolated from the fresh water blue-green alga Aphanizomenon f los-aquae starting from a suitable cyclic sulfamate.607,608 Sulfamates 229 and 230 are key

from L-serine methyl ester, and it is thermally stable 140 references) titled “sulfamates and their therapeutic potential” covers not only CA inhibition by sulfamates but also inhibition of steroidal sulfatases, and there are sections on anticonvulsant, antiobesity sulfamates, and other relevant areas.652 Another long review in 2006 from the same group covered CA inhibitors (CAIs) and activators and their use in therapy (145 references).653 They also wrote two shorter articles on “targeting tumor-associated CA IX in cancer AD


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multiphasic aspects of CA inhibitors and activators from the perspective of drug design. Some of these chapters are relevant to this review in that they have quite a few examples dealing with sulfamates playing an inhibitory role. For example, Chapter 3 on “zinc binding functions in the design of carbonic anhydrase inhibitors” has numerous illustrations of new sulfamate esters, binding data, and illustrations of the binding mode of some to CA active sites.666 A series of four sulfamates NH2SO2O−R (R = nBu, n-hexyl, cyc-hexyl, and Bn) together with topiramate 10 and the topiramate cyclic sulfate 277 have had their inhibitory activity with CA II isoform assessed and explained using molecular modeling techniques. The inhibitory activity is linked to positive interactions with the ligand and to the solvation pattern of each ligand.667 p-Chlorophenylsulfamate, 1,8-octyl bis-sulfamate, and topiramate have had their inhibitory activity assessed against bsCA I and bsCA II, the β-CA from the bacterial pathogen Brucella suis.668 Various small anions such as sulfamate and NH(SO3)22− showed inhibitory activity when assessed against two new β-CA enzymes from the bacterial pathogen Salmonella enterica serovar Typhimurium.669 Sulfamate also showed strong inhibitory effects on CA from the gill of the European seabass, and the susceptibility to various anions differs significantly between fish and mammalian CAs.670 A review of small anions as CA inhibitors has appeared recently.671 Recently, a series of novel carbohydrate sulfamates based on the scaffold 278 has been synthesized and their inhibitory activity examined toward CAs IX and XII. These sulfamates were derived from the monosaccharides D-glucose, D-galactose, D-mannose, and methyl α-glucopyranoside and the saccharide maltose, all of which bear acetyl groups and in some cases propionyl and butyryl groups. The results indicate that these carbohydrate sulfamates have considerable potential in medicinal chemistry.672 The inhibitory activity of a series of 11 mono-, di-, tri-, tetra-, and perfluorophenyl sulfamates has been examined using again the CAs IX and XII.673 5.1.4. Topiramate and Related Compounds. 5.1.4.1. Reviews, X-ray, and Other Studies. The story of the discovery and development of topiramate 10 the anticonvulsant and antiobesity drug has been told relatively recently by Maryanoff,

The crystal structure of 277 with hCA II has also been published, and it was shown that the inhibitor coordinates to the active site zinc ion through its oxygen atom and the ionized nitrogen atom by replacing water molecules.677 β-CA from Helicobactor pylori hpβCA strongly inhibited topiramate, and this was the first study showing that a bacterial β-CA can be a drug target,678 and topiramate was also inhibited by a β-CA from Brucella suis bsCA I.679 A CA II inhibition study that compared the effectiveness of bioisosteric sulfamates (X = O) and sulfamides (X = NH) in 279, 280, and 281 and in topiramate 10 and the cyclic sulfate 277 with their sulfamide analogs, i.e., replacing the oxygen attached to the side-chain −CH2 groups in each with −NHs, found that the sulfamates were much more potent by factors ranging from 25 280 (X = O)/280 (X = NH) to 1200 but mostly closer to the lower figure680 (see section 5.1.4.3 below). Some years ago in a major structure−activity study of topiramate the Maryanoff group probed the potencies of a more than 100 analogs. This resulted in the synthesis of compounds where alterations were made in the sulfamate side chain, the linker between the sulfamate group and the core pyran ring, the substituents on the two dioxolane rings, the make up of the 4,5-fused 1,3-dioxolone ring, the ring oxygen atoms, and the absolute stereochemistry. X-ray crystals structures were reported for 10, for 277 (RWJ-37947), for 10 with a methyl group replacing one of the hydrogens in the side-chain −CH2 group, and for 282.681 5.1.4.2. Synthesis. The first report on the synthesis and anticonvulsant and other properties of topiramate 10 and a series of analogues was given in 1987.682 Preparation of the chlorosulfate of 10, 683,684 of the topiramate analogues represented by 283 (with X = C, S; R1, R2 = H, alkyl, cycloalkyl, allyl, Bn; R3, R4 = H, alkyl, etc.),685 each of which does not have the pyran ring oxygen, and of hydroxylated derivatives of 10 has been reported.686 Other topiramate derivatives prepared include a sodium trihydrate,687 a derivative for treating acute ischemiainduced neurodegeneration caused by stroke, head trauma, cardiac arrest, and major surgical procedures,688 and analogs which can be used in immune-diagnostic assays to compete with 10 for binding with antitopiramate antibodies.689 A number of processes for preparation of 10 have been patented. Reaction of sulfamic acid with diacetone-β-fructose gave 10.690 A continuous process for preparation of 10 involves similar reaction with sulfuryl chloride followed by reaction with ammonia.691,692 A quantitative yield of 10 has been reported in another patent.692 In a variation of this, sulfamoyl chloride in DMA in the presence of N-methylmorpholine has been used to effect the sulfamoylation reaction.693 A convenient one-pot synthesis of 10 giving a 55% yield has been reported via use of chlorosulfonylisocyanate, diethylamine, and 2,3:3,4-bis-O-(1methylethylenidene)-β-D-fructopyranose.694 The sulfamate group was essential in the reaction of 10 with polyethylene glycol 8000 (PEG), giving a new polymorphic form which was investigated using differential scanning calorimetry (DSC), FT-IR, and solid-state NMR.695 A number of papers dealing with determination of 10 have been discussed earlier (see section 2.9).167−171 5.1.4.3. Inhibition. Inhibition of CA II by 10 and its cyclic sulfate 277 has been compared with its inhibition by their sulfamide analogs, i.e., 10 and 277, in which the oxygen attached to the side-chain −CH2 groups in each is replaced with −NHs. As previously found,680 when the two bioisosteric pairs were compared the sulfamates were much more potent than the

who was intimately involved and whose name is synonymous with it. His 12-page review with more than 100 references covers inter alia the earlier years, clinical development, the mechanism of action, and regulatory approval and commercialization.674 The crystal structures of 10 and several related sugar sulfamates 104, 105, and 106 have been reported (see section 3.1).422 The crystal structure of the adduct of hCA II and 10 has been reported,675 and homology modeling and molecular dynamics simulation has shown what the structure of the complex is.676 AE


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[CH2OH]nOSO2NH2 have also been used as antiglaucoma agents.710 Compound 290, which is a new type of oral antiarthritic agent,711 was synthesized in 85% yield from the precursor diol with N-methylsulfamoyl chloride and EtN(iPr)2 in CH2Cl2, and its S(−)- and R(+)-isomers were prepared similarly from the appropriate optically active diols.

sulfamides.696,697 Compound 10 has been shown to be an effective inhibitor against various CAs in tests that also included a library of sulfonamides, some of which were less effective than 10. Thus, 10 was an effective inhibitor of mitochondrial hCA VB,698 of hCA VI,699 of the two β-CAs from the bacterial pathogen Salmonella enterica serovar Typhimurium stCA I and stCA II,700 and of the β-CA encoded by the gene Rv 1284 (mtCA I) of

5.2. Steroidal Sulfatase Inhibitors (SSIs)

5.2.1. Reviews. The phenomenal interest in this area is reflected in the large number of reviews that have come out and continue to appear regularly. Earlier short reviews712−716 are still useful and help to set the scene for developments that have taken place since then. A comprehensive review on steroid sulfatase inhibitors (85 references) appeared in 1999,717 and in 2004 a review (>200 references) on the same topic718 appeared. A review (318 references) on steroid sulfatase, molecular biology, regulation, and inhibition, was published in 2005.719 Also in 2005 a review as a book chapter on enzyme inhibitory examples for treatment of breast cancer appeared.720 A short review on estrone sulfatase and its inhibitors was published in 2005.721 Two more recent reviews both having almost 80 references highlight sulfatases as anticancer inhibitors.722,723 Two important very

Mycobacterium tuberculosis701 and showed medium potency against Helicobacter pylori α-class CA (hpCA).702 A series of eight carbohydrate sulfamates 284 and 285 derived from D-glucose, D-galactose, and D-mannose with the sulfamate on the C-6 primary hydroxyl group and with the other four hydroxyl groups free (in 284) or acetylated (in 285) or propionylated or butyrylated have been complexed with human CA II and X-ray crystallographic structures obtained for four acetylated complexes. Surprisingly, a free hydroxyl group was seen at the anomeric center (C-1), and this group was axial to the carbohydrate ring, while the parent structure is equatorial. Sequential loss of the four acyl groups could be observed using ESI-FTICR-MS. It is suggested that the substrate binding mode dominates, but after hydrolysis the ligand can also bind as a pure inhibitor, thus competing with the substrate binding mode.703 5.1.5. Other Medicinal Uses. The phenylethylsulfamates, R−C6H4CH2CH2OSO2NH2, have been patented as anticonvulsant and antiglaucoma agents.704 Compounds such as 286 made from phenol and ClCH(CO2Et)2 followed by reaction of the intermediate C6H5OCH(CH2OSO2NH2)2 with NH2SO2Cl showed promise as anticonvulsants.705 “Dual” sulfamate/ carbamate compounds 287 have been synthesized and are useful for central nervous system diseases such as epilepsy, myalgia, etc.706 Sulfamate esters of type 288 (X = CH2, O; R1 = alkyl, H; R2−R5 = H, lower alkyl, etc.) are used for treating impulse control disorders.707 The p- and m-imidazole-substituted phenyl- and phenoxysulfamates 289 (Im = C3H2N2− and MeC3H2N2−; n = 0, 2, 3) are antiglaucoma agents.708 A little later identical and similar compounds have been reported from the same laboratory as antiglaucoma agents; they include compounds with methyl substituents in the phenyl ring and a m-chloro substituent in the imidazole ring. 709 Aryloxyalkylsulfamates of type ArO-

recent reviews (both with ∼125 references) from the Poirier724 and Potter725 groups deal with developments in steroid sulfatase inhibitors. There is as noted above a good section on “sulfamates as inhibitors of steroid sulfatases” in a review on “sulfamates and their therapeutic potential”.652 Finally, some years ago a lengthy review (>300 references) on sulfatases, structure, mechanism, biological activity, inhibition, and synthetic utility, was published.726 5.2.2. Introduction. Many of the reviews cited above trace the history of the development of steroidal sulfatase inhibitors (SSIs), and it is unnecessary here to cover this ground again. Suffice it to say that by far the most important development in this field was the discovery in the early 1990s that estrone-Osulfamate, emate 111 was a potent steroidal sulfatase inhibitor (see for example, ref 712). Much of the work since then has focused on synthesis and testing of many analogs of 111 as SSIs, and this compound has served as a template in devising routes to new potential inhibitors. Compound 111 is represented here now as structure 291 in which the four rings are identified as A, B, C, and D, and the main positions have been numbered, and this structure affords a convenient framework for outlining modifications that have been made in the A and D rings. Synthetic difficulties that arise when trying to substitute the B and C rings means that little has been done with these. Structure 291 also helps to represent other changes that have been made such as disubstitution, enlargement, other changes in the D ring, and formation of bis-sulfamates for example. 5.2.3. Substitution in the A Ring at the 2 and 3 Positions. Generally the most successful analog of emate is considered to be 2-methoxyestrone 3-O-sulfamate 291 (R1 = OMe, R2 = R3 = H), 2-MeOemate, which showed good activity toward cancer cells. Analogs of 291 with R1 = SMe and Et AF


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showed much reduced inhibition.727 The series 291 (R1 = F, Cl, Br, I; R2 = R3 = H)728 and 291 (R1 = CHF2; R2 = R3 = H)729 have been made, the latter having an IC50 of 100 pM against steroidal sulfatase, which is about 90-fold lower than emate obtained from the same assay. Compounds 291 (R1 = R2 = F, R3 = Me, Ph; R1 = R2 = Cl or Br, R3 = Me, Ph) have been synthesized and found to inhibit both steroid sulfatases and aromatase enzymes.730 A saturated A ring in 291 in conjunction with 17 substitution in the D ring has been looked at.731 Other changes made in 291 include replacing the NH 2 SO 2 O− group with MeNHSO 2 O−, Me2NSO2O−732 and BnNHSO2O−, NH2SO2S−, C5H10NSO2O, Bn2NSO2O−, RCONHSO2O− (R = Ph, Me, and Et; R1 = R2 = R3 = H).733 In both studies 111 was also included, and none of the new derivatives were as effective as 111 in inhibition studies with MCF-7 breast cancer cells. 5.2.4. Substitution in the D Ring at the 17 and Other Positions. Structures 291 with the C-17 carbonyl reduced to OH− and introduction of a 4-tert-butylbenzyl,734,735 4-iPrphenyl,734 or Bn735 at the same position have been synthesized and tested for their ability to inhibit steroidal sulfatase. The C-17

Figure 1. (a) Benzimidazole, (b) oxazole, (c) triazole, and (d) tetrazole.

The Poirier group carried out solid-phase parallel chemistry using the steroid 292 to generate two libraries of 25 phenols and 25 corresponding sulfamates 293. Compounds from both libraries were examined for steroid sulfatase inhibitory activity, and those sulfamates with a 3-cyclopentylpropyl moiety showed inhibitory activity similar to other known inhibitors.444 The Poirier group assembled libraries of 16β-aminopropyl estradiol derivatives of phenols and sulfamates each containing 48 compounds using solid-phase parallel chemistry via a sevenstep reaction sequence.742

carbonyl has been replaced by the amide substituent −C( O)N(iPr)2 and a double CC bond between C-16 and C-17 to give a compound known as KW-2581, which inhibited sulfatedestrogen-dependent growth of breast cancer cells.736 Again, carbonyl group replacement, introduction of a C-16/C-17 double bond, and placing an acetyl group at the 17 position in 291 gave a compound which showed estrone sulfatase inhibitory activity of IC50 = 21 pM,737 and placing a −C(O)NHnPr group there gave IC50 of nM.738 Other emate derivatives substituted at the 17 position with amide groups include those with the carbonyl bond replaced with −C(O)NH(CH2)nMe, n = 6−9, −NHC(O)(CH2)nMe, n = 6−9, −(CH2)2NHCO(CH2)12Me,739 and −C(O)N(nPr)Me.740 These compounds may be useful for treating estrogen-dependent breast cancer. Replacing the carbonyl group in 291 with successively −C( O)Me, −CH(OH)Me, −C(OH)CH2C6H4-tBu-4, and −C(OH)MeBn gave compounds which had somewhat higher percent steroid sulfatase inhibition,731 and similar replacement with −(CH2)2O(CH2)2NEt2 at C-17 gave a compound known as SR 16157 which is actually a dual target compound exerting steroid sulfatase inhibition and antiestrogenic effects.741

The five sulfamates 291 with R2 = R3 = H and with the CO at C-17 replaced with −COMe and −CH2COMe (R1 = MeO, Et) and −CH2C(OH)Me (R1 = MeO) have been synthesized by the Potter group. The two acyl, two 2-propoxy, and 2hydroxypropyl compounds all displayed excellent antiproliferative activity in vitro against a broad range of cancer cells.743 In 291 with R2 = R3 = H replacement of the CO at C-17 with a cyanomethyl group and with R1 = MeO, Et again gave compounds with potent antiproliferative effects.744 Introduction of various heterocyclic groups at C-17 has been explored. 745 A double bond between C-16 and C-17, replacement of the carbonyl at C-17 with a benzimidazole (Figure 1a), and replacement of the CO at C-17 with oxazole, triazole, and tetrazole groupings746 (Figure 1b, 1c, and 1d) and R1 = Et, R2 = R3 = H in 291 gave four new compounds. A study AG


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with the benzimidazole compound did not show a significant effect on LAPC-4 tumor growth.745 Toxicological data was available for the oxazole, triazole, and tetrazole, the compounds based on determinations against DU-145 human prostate cancer cells, MDA-MB-231, and MCF-7 human breast cancer cells.746 An unusual example of substitution in the C ring at carbon-11 is shown in 294, which was synthesized through cleavage of a disulfide precursor. Compound 294 was synthesized as a hapten for development of an enzyme immunoassay for estrogen sulfamates.747 In a patent the same group described the synthesis of some estra-1,3,5,(10)-trien-3-yl sulfamate derivatives with substituents in the B and C rings. No data was provided on any inhibitory activity.748 In another patent they made various 2-substituted alkoxy and fluoroalkoxy sulfamates of type 291 with R1 = C1−4-alkoxy, -fluoroalkoxy, and the C-17 carbonyl replaced with −OH,

sulfamates. Compounds 297 show inhibitory activity toward estrone sulfatase and inhibit growth of MCF-7 human breast cancer cells.755

Two sulfamates 299 and 300 where the D ring is doubly substituted at C-16/C-17 have been reported, but no biological data are given,756 but 13C NMR data on these compounds and the parent estrones have been reported.757 In a patent the same researchers describe D-ring enlargement and substitution at various sites in the B, C, and D rings, giving compounds such as 301.753 Reed discussed changes in the D and A rings in a review (32 references) some years ago.758 Two highly potent steroid sulfatase inhibitors 302 (R = nPr, 1-pyridin-3-ylmethyl) which are superior to emate 111 have been reported by the Potter group.759 They greatly extended this work using other R substituents on the nitrogen in 302, but the two compounds mentioned are the best inhibitors.760 5.2.6. Bis-Sulfamates. The bis-sulfamate 290 which is an oral antiarthritic agent has been mentioned earlier,711 and work on the anticonvulsant phenoxy bis-sulfamates PhOCH(CH2OSO2NH2)2 has also been cited.705 There has been much interest in the estradiol derivatives 2-methoxyestradiolbis-sulfamate (2-MeOEbisMATE 303, R = MeO) and 2ethylestradiol-bis-sulfamate (2-EtE2bisMATE 303 (R = Et). It was found some years ago that breast cancer cells that are resistant to conventional chemotherapy remain sensitive to these 2-substituted estrogen sulfamates.761 Other studies have compared the abilities of 303 (R = MeO) and the parent steroid 2-MeOE2 304 to inhibit growth of MCF-7 breast cancer cells762 and looked at in vitro effects of 303 (R = MeO) on the nontumorigenic MCF-12A line cell763 and on cell growth, morphology, and cell cycle dynamics in the MCF-7 breast adenocarcinoma cell line.764

O(C1−4-alkyl), O(C1−11−acyl), OSO2NRR. These compounds can be used for treating prostatic carcinoma.749 Various sulfamates 291 with a methyl group at C-15 of the D ring and the carbonyl double bond at C-17 replaced with −OH, C1−5alkyl, C1−5-alkoxy have been described.750,751 Further work by the Poirier group has led to development of a library of 30 sulfamates 295 synthesized in ∼50% yields from NHFmoc-protected precursors.752 An acetyl group was introduced at C-17, replacing the CO, and the 3α- and 3β-sulfamates of the steroids 20-oxo-5αpregnan-3α-yl, 20-oxo-5α-pregnan-3β-yl, 20-oxo-5β-pregnan3α-yl, and 20-oxo-5β-pregnan-3β-yl were prepared from the corresponding 3α- and 3β-alcohols, giving compounds 296, and their interaction with the gamma-aminobutyric acid subtype GABAA has been studied.376 A series of gonane sulfamate derivatives with D-ring enlargement in some cases and substitution in the B, C, and D rings has been reported in a patent.753 An unusual C-15 D-ring substitution in 291 has been reported in which a −(CH2)1−6CONRR was introduced.754 5.2.5. Major Changes in the A and D Rings. Peters’ group synthesized a series of steroidal oxathiazine inhibitors 297 of estrone sulfatase in which a profound change has been made in the A ring, and a diverse series of substituents has also been introduced at the C-17 position. They also made a comparable series of compounds 298. Both 297 and 298 are in effect cyclic AH


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Compound 303 (R = MeO) with radiolabeled carbon-11 on the methoxy side chain carbon has been prepared by carbon-11 methylation of 2-hydroxyestradiol-3,17β-O,O-bis(N-trityl)sulfamate with 11CH3I followed by detritylation. Uptake of this radiolabeled compound by human umbilical vascular endothelial cells (HUVECs) is less than that of the unlabeled compound.765 Synthesis of another radiolabeled compound with >99% radioactive purity 16α[18F]fluorestradiol-3,17β-disulfamate 305 (R1 = R2 = NH2SO2O) and of the monosulfamates 305 (R1 = NH2SO2O; R2 = H) and 305 (R1 = H; R2 = NH2SO2O) has been reported. The disulfamate has a high sulfatase inhibitory activity, and it is hoped that the radio fluorocompound can image the active sites of sulfatase by positron emission tomography.766,767 Various other radiofluorocompounds related to 305 have been reported in a subsequent patent.768 Aliphatic bis-sulfamates NH2SO2O-n-C8H16OSO2NH2 and NH 2 SO 2 O-n-C 10 H 20 OSO 2 NH 2 and the monosulfamates nC8H17OSO2NH2 and nC10H21OSO2NH2 and their detailed inhibition profiles against the isoforms CAs I−XIV have been

sulfamate.771 The synthesis, antitubulin, and antiproliferative structure−activity relationships (SARs) of analogs of 303 in which the C-17 sulfamate moiety is replaced by −OSO2Me in 303 (R = MeO, Et) and −OSO2Me and −CH2SO2Me in 303 (R = Et) have been reported. A SAR has been established for various 2-substituted estradiol-3-O-sulfamate derivatives based on their ability to inhibit tubulin polymerization.772 5.3. Nonsteroidal Sulfatase Inhibitors (NSSIs)

5.3.1. Reviews. The two recent reviews724,725 cited above in section 5.2.1 have sections on nonsteroidal sulfatase inhibitors, and an earlier review652 is also useful for NSSIs. Quantitative SARs have been found for nine subsets of NSSIs, such as 307 with X = −(CH2)3CO−, −(CH2)2OCO−, −(CH2)2NHCO−, etc., using measured IC50 for each compound for inhibition of estrone sulfatase, calculated log P values, and calculated molar refractivity as variables. When all subsets are combined giving a database of 101 compounds a correlation coefficient r = 0.912 was obtained.773 5.3.2. Phenyl and Biphenyl Compounds. Compounds of type 308 with various linkers between the aromatic rings including CC, CC, and varying amide moieties and various heterocycles have been patented as being useful for prevention and treatment of breast cancer, endometrial carcinoma, ovarian cancer, and prostate cancer.774 The cyclic sulfamate compounds 309, n = 1, 2, inhibit sulfatases in a mechanism-based fashion.775 The Ahmed group patented a series of compounds of type 310 (R1−R5 = H, halo, cyano, aryl, etc., X = O, S, NH, etc., and R6 = H, alkyl, alkoxy, aryl, etc.) which inhibit estrone sulfatase and dehydroepiandrosterone sulfatase. Typical compounds made include 310 with R1, R2, R4, and R5 all H, R3 = NH2SO2O−, X = O, and R6 = Me, Et, n-heptyl, and n-octyl.776 The same researchers prepared a series of 23 simple phenyl- and alkylsulfamates NH2SO2OR, with typical R’s being p- and mMe, F, Cl, Br, I, CN, and NO2-phenyl and C6H5− and Me(CH2)5−7CH2− and XCH2− where X = Cl3C−, Cl2CH−, and ClCH2−. The phenylsulfamates were shown to be better than the alkyl compounds as inhibitors of estrone sulfatase, and one of them, NH2SO2OC6H4NO2-m, had a percent inhibition approaching that of emate 111 and 4-methylcoumarin-7-Osulfamate, known as coumate (see section 5.3.6), which were included in the study.777 A mechanism for inhibition of estrone sulfatase by sulfamates has been proposed in which the crucial step is cleavage of the S−OR bond by attack of the sulfamate at the gem-diol moiety at the active site of estrone sulfatase.778 4Sulfamated phenylketones 311 have been prepared, and a SAR using IC50 (for estrone sulfatase inhibition) and log P (for the parent phenols) data shows that they are often more potent than coumate but weaker than emate 111. There is a good nonlinear correlation (r2 = 0.98) between IC50 for six of the alkyl compounds and log P in a quadratic equation.779 A good nonlinear correlation (r2 = 0.729) of another type was obtained

reported. X-ray crystallographic structures in the adducts with isoform II and molecular modeling studies with hCA IX have also been published. Bis-sulfamates showed a better affinity for hCA IX than for hCA II, but the reverse was true for the monosulfamates.769 Compound 303 (R = H) E2bisMATE and 303 (R = MeO) may share a common mode of binding to tubulin based on modeling studies. Compound 303 (R = MeO) was cocrystallized with CA II, and X-ray showed unexpected coordination of the 17O-sulfamate of 303 (R = MeO) to the active zinc site.432

A series of bis-sulfamates, NH2SO2O−R−OSO2NH2 (R = (CH 2 ) 4 , 6 − 8 , 1 0 , 1 2 , 1 6 , CHMeCHMe, CH 2 CMe 2 CH 2 , 4CH2C6H4CH2, betulinyl, etc.), were readily made by the Supuran group using sulfamoyl chloride and the appropriate diols/ phenols. This library was then tested against the hCA isozymes, the cytosolic hCA I and II and hCA IX.770 A number of other compounds of type 303 have been synthesized with R = Me, nPr, iPr, nBu, and tBu, and a series of monosulfamate/monocarbamate derivatives 306 with R = H, Me, OMe, Et, nPr, iPr, nBu, and tBu has been synthesized. Surprisingly, in the 306 series compound 306 (R = MeO) is 13fold weaker as an steroid sulfatase inhibitor than the parent bisAI


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and evaluating some cycloalkyl esters, i.e., 311 with R = OMe to O-n-decyl- and O-cyc-pentyl to -cyc-octyl, as sulfatase inhibitors and found that 311 (R = O-cyc-octyl) was a better inhibitor than coumate.787 The study was broadened further by synthesizing a series of sulfamates of cinnamic (313, R = −CHCH2(C O)OR1 with R1 = Me, Me(CH2)1−8) and propionic 313 (R = −(CH2)2(CO)OR1 with R1 = Me, Me(CH2)1−8) acids and assessing their IC50 values. The trans-4-cinnamates are weaker inhibitors of estrone sulfatase than the standards (111, coumate, and 667-coumate) used, and the propionates were extremely weak inhibitors of estrone sulfatase.788 Above in section 5.3.2 the ketones 311 (R = H, Me, Bn, PhCHCH, Ph, and various alkyls), which can also be classified as phenyl derivatives, have been discussed already.779 Nussbaumer made a series of benzophenone sulfamates 314 (with R = H, 2-, 3-, 4-MeO, 2-, 3-, 4-OH, 3- and 4-NH2SO2O and in the other ring the sulfamate group can be in either the 3 or the 4 position) with a view to assessing their potencies as estrone sulfatase inhibitors. The 4,4′-benzophenone-O,O′-disulfamate (known as BENZOMATE) showed the greatest activity (rivaling 111) and more than that of any of the 3- and 4-substituted benzophenone-O-sulfamates. The other two disulfamates synthesized also showed good activity.789 The Potter group explored the potential of various benzophenone sulfamates and disulfamates further by synthesizing compounds such as 315

Figure 2. Biphenyl compound (A) mimics the A and C rings of the steroid backbone of emate (B).

between IC 50 values (estrone sulfatase inhibition) for NH2SO2OC6H4-X-m or -p and pKa values of eight parent phenols.780 The phenyl compounds 312 with R1 = R2 = H, lower alkyl, R3 = H, lower alkyl, halo, lower alkanoylamino, etc., A = (un)substituted Ph, naphthyl, pyridyl, and other hetero have been patented as excellent steroid sulfatase inhibitors.781 Three of the papers cited above also include some biphenyl compounds.776,779,780 The biphenyls p-RC6H4−C6H4OSO2NH2 with R = −CO2H, −CONR1R2, −CONR1OCH2Ph, COR2, etc., are steroidal sulfatase inhibitors.782 A set of sulfamate biphenyls pNH2SO2OC6H4−C6H4−R (R = 2′-CN, -NO2, -CF3, -Me; 3′NO2; 4′-CF3, -Br, -Cl, -OMe, -NO2, -CN, -OH, -OSO2NH2) were synthesized, and it was found that those with electronwithdrawing groups at the 2′ or 4′ positions increased inhibition activity, for example, the 2′,4′-dicyano compound showed very potent inhibitory activity in vitro. This compound known as TZS-8478, being a potent steroidal sufatase inhibitor without estrogenicity, was an important discovery.783 Further studies by

the same workers showed that this compound inter alia completely inhibited steroidal sulfatase activity in tumors, uterus, and liver and lowered plasma concentrations of estrone and estradiol.784 A rationale for the synthesis and molecular modeling study of 4′-O-sulfamate-4-biphenyls is shown in Figure 2, where it is seen that the biphenyl compounds could allow mimicking of the A and C rings of the steroid backbone in emate 111 and might therefore prove useful as inhibitors. Biochemical evaluation showed that this is indeed the case, and they possess greater inhibitory activity than 667-coumate (see section 5.3.6) but less than emate 111.785 5.3.3. Benzoic and Cinnamic Acids and Ketones. A range of benzoic acid-substituted sulfamates 311 with R = Me(CH2)nO− (n = 0−9) have been synthesized and evaluated by the Ahmed group as possible sulfatase inhibitors. It was found that they possess lower activity than 667-coumate but higher activity than emate 111.786 They extended their study by making

with X = NH2SO2O− and R = H, −OH, and 316 X = NH2SO2O−. Other changes included replacing the bridgehead carbonyl with sulfide and sulfone with longer linkers such as −CHCHCO. BENZOMATE is a highly potent inhibitor both in vitro and in vivo, and it and the other compounds in this group represent an important class of NSSIs.790 Thiosemicarbazone-based compounds 317 with R = H, 2-, 3-, 4-Cl; 2-, 3-, 4-Br; 2-, 3-, 4-NO2; 2-, 3-Me turn out to be weak inhibitors of estrone sulfatase and not at all in the same league as the standards, 111 and coumate.791 5.3.4. Heterocycles. Compounds 318 as benzoxazoles (X = O) and benzothiazoles (X = S) have been described in a patent and are important as inhibitors of steroid sulfatase being comparable to emate 111.792 Compound 319 was a typical and promising example of those synthesized (in 45% yield) and found to be a potent irreversible inhibitor of steroid sulfatase.793 AJ


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suitable for treatment of androgren- and estrogen-dependent diseases.796 A series of 2-phenylindole sulfamates 322 (R1 = Et, −(CH2)6NC4H8, −(CH2)5CONC4H8, −(CH2)10SO2C5H11; R2 = H, OH, NH2SO2O−; R3, R4 = H, NH2SO2O−) has been

The same authors made a new class of NSSIs, the 2-substituted 4(thio)chromenone 6-O-sulfamates, represented generally by

synthesized as antiestrogen-based inhibitors of steroid sulfatase in human breast cancer cells.797 Later the same authors798 synthesized other 2-phenylindole sulfamates with lipophilic side chains giving compounds 322 with R1 = Me, Et, nBu, n-heptyl, ndecyl; R 2 , R 4 = H, NH 2 SO 2 O−; R 3 = H, −CONH 2 , −CONHC8,10,12H17,21,25. Benzothiophene sulfamates as steroid sulfatase inhibitors have also attracted attention. Compound 323 was comparable to 111 as an inhibitor based on its IC50 value, and in a uterotropic assay in rats for residual estrogenoic activity it was dissimilar to 667-coumate.799,800 Flavone, isoflavone, and flavanone represented by structures 324 and 325 with at least one sulfamate moiety attached801 and benzopyransulfamates 326 with a sulfamate group802 have been patented as steroid sulfatase inhibitors. Some piperazinylphen y l s u l f a m at e s , t y p i c a l l y 3 2 7 , 8 0 3 a nd so m e 4 -( 2 carbamoylethenyl)phenylsulfamates such as 328804 act as steroid sulfatase inhibitors. 5.3.5. Tyramine Derivatives. The Li group developed a series of tyramine-based sulfamate NSSIs 329 with n = 5−13805 which were effective steroidal sulfatase inhibitors, and those with n = 11 and 12 were superior with IC50 values of ∼58 nM.805,806 In extending their studies 329 (n = 11) with the −(CH2)2NHCO− moiety replaced with −CH2CH2O, (CH2)3CO, (CH2)3CH(OH), and (CH2)3CH2 were synthesized, but each turned out to have much higher IC50 values than compounds 329 (n = 11, 12).807 A related set represented by compounds 330 with m = 0 and n = 6, 8, 10, 12, m = 1 and n = 6, 8, 10, 12, and m = 3 and n = 6, 8, 10, 12, and 14 had IC50 values much larger than compounds 329.808 Interestingly, compounds 330 with the two hydrogens of the sulfamate replaced with alkyl groups could enhance memory in patients with memory loss including amnesia, Alzheimer’s disease, etc.809 The (E) and (Z) isomers of 4-hydroxytamoxifen sulfamates 331 inhibit estrone sulfatase from rat liver competitively.810 Series of 17β-(N-alkylcarbamoyl)-estra-1,3,5(10)-trien-3-Osulfamates 332 (R = −CONH(CH2)6−9Me) and 17β-(Nalkanoyl)-estra-1,3,5(10)-trien-3-O-sulfamates 332 (R =

compounds 320, and they found the most potent inhibitor (170 times more potent than 111) to be 320 with X = S, R = 1adamantyl and NH2SO2O− at the 6 position with an IC50 of 0.34 nM compared to 111 which was 56 ± 8 nM in their assay. More than 25 other related compounds were synthesized all based on the template 320 with X = O, S and a large number of alkyl and alicyclic substituents (R) and the sulfamate moiety occupying

either the 6 or the 7 position.794 Further work in which 10 additional compounds 320 were synthesized led to the discovery of 321 with the substituent 4-pentylbicyclo[2.2.2]-oct-1-yl in the 2 position. This compound lacks estrogenicity but is a potent inhibitor and has an in vitro profile which indicates that it is ideal for treatment of breast cancer.795 These researchers proposed 6-[2-(adamantylidene)-hydroxybenzoxazole]-O-sulfamate 319 (with a CC between the bridgehead of the adamantyl ring and C-1 of the side chain) as AK


Chemical Reviews

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bit less active than their steroidal analogues, are more potent than emate 111.816

−NHCO(CH2)6−9Me), both of which are modeled on emate 111, have been synthesized and show promise as inhibitors of breast cancer cell estrone sulfatase activity.739 5.3.6. Tricyclic Coumarin Sulfamates. 4-Methylcoumarin7-O-sulfamate, known as coumate, 333 (with R1 = R3 = H; R2 = Me), was synthesized and is free of estrogenic activity unlike

In vitro metabolism of 334 (n = 5) or 667-coumate (also known as Irosustat or STX64 or BN83495) has recently been examined, and it was found that 667-coumarin, the desulfamoylated derivative of 667-coumate, was formed by degradation and also by non-NAPPH-dependent enzymatic hydrolysis.817 In a recent important SAR study the sulfamate hydrogens have been replaced by methyl groups in 667-coumate, the sulfamate group has been relocated to another position and flanked with an adjacent methoxy group, the size of the alicyclic ring has been looked at, and a series of quinolin-2(1H)-one and quinolone derivatives of 667-coumate was made. The sufatase inhibitory activity of the new derivatives was assessed using a preparation of JEG-3 cells.818 5.3.7. Dual Aromatase−Steroidal Sulfatase (DASI). The Potter group developed dual aromatase−steroidal sulfatase inhibitors (DASIs) 337 (R1 = NH2SO2O−, R2 = H, F, Cl, Br; R1 = H, R2 = NH2SO2O−). The key roles of these compounds is that they have the capacity to block (a) the aromatase enzymes which produce estrogens and (b) the sulfatase enzymes which hydrolyzes estrone sulfate to estrone producing a major supply of estrogens in tumors. The 337 fluoro, bromo, and chloro compounds are 5−11-fold more active than 337 (where R2 = H) in sulfatase inhibition and in aromatase inhibition about 8− 120-fold more active.819 They also developed a series of benzyltriazole derivatives 338 based on a template of anastrozole, an established aromatase inhibitor. The compound with the highest potency was found to be 338 with R1 = R2 = Me; R3 = H.820 The related triazole-based compounds 112 (R1 = NH2SO2O−; R2 = F and R2 = Br, R1 = NH2SO2O−; R3 = H) stood out as DASIs from a series synthesized.431

emate 111, and it is a potent NSSI.811 This has led to considerable interest in other similar derivatives, and thus, 333 with R1, R2, R3 = H, H, H; H, Me, H; Me, Me, H; Me, Me, Me; and H, CF3, H have been made and assessed. These compounds were good inhibitors of estrone sulfatase, being up to 93% for coumate, which was also found to be devoid of any estrogenic activity in contrast to emate 111812 These discoveries spurred on further work on coumarin derivatives, and others synthesized and tested include 333 (with R1 = R3 = H, R2 = Et; R1 = R3 = H; R2 = nPr; R1 = Et, R2 = Me, R3 = H; R1 = nPr, R2 = Me, R3 = H), compounds 334 (n = 3−6), and the tricyclic oxepin sulfamate 335. Compounds 334 are known as 665-coumate (n = 3), 666-coumate (n = 4), 667-coumate (n = 5), and 668-coumate (n = 6). All of these compounds were found to be more active than the parent coumate, i.e., 333 (with R1 = R3 = H, R2 = Me), with the most potent inhibitor being 667-coumate, which is not estrogenic.813 A phase 1 study of 334 (n = 5), i.e., 667-coumate, also known as STX 64 in breast cancer patients, has shown promise.814 Further synthesis gave 334 with n = 7−13 giving 669-coumate (n = 7), 6610-coumate (n = 8), 6611-coumate (n = 9), 6612coumate (n = 10), 6613-coumate (n = 11), and 6615-coumate (n = 13) and the size of the third ring had a strong effect on the inhibitory properties of the compounds, the most potent being 6610-coumate with an IC50 of 1 nM.815 The Poirier group synthesized the phenyl tert-butylbenzyl 5alkanols 336 which incorporate some structural features from previously known steroidal sulfatase inhibitors. The best 336 inhibitors were the undecanol analogs, and these NSSIs, though a AL


Chemical Reviews

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Compound 339 (with R1 = NH2SO2O−, R2 = MeO and with Cl at the 2 position) has been synthesized with carbon-11 radiolabeling at the MeO and CN sites as a new potential positron-emission tomography DASI.828

Recently, the Potter group described some sulfamate DASIs derived from letrozole and vorozole templates. Compounds 344 and 345 are close analogs of letrozole and vorozole, respectively. In the case of the former it is the most potent DASI among achiral and racemic compounds with IC50 (aromatase) = 0.87 nM and IC50 (sulfatase) = 593 nM. Enantiomers of 344 were separated starting from the precursor phenols, and the S(+)sulfamate inhibited aromatase and sulfatase most potently.829 5.4. Other Medicinally Important Esters

Recently, a novel dual-acting inhibitor of estrogen action that irreversibly inhibits steroidal sulfatase (STS) and releases the estrogen receptor modulator SR 16137 339 has been

5.4.1. Carbohydrate, Amino Acid, and Peptide Sulfamates. The cyclic sulfamate 346 was synthesized in 60% overall yield from L-serine benzyl ester, HOCH2CH(NH2)CO2Bn.

described.821 The triazole derivative 340 as the (S)-sulfamate inhibited sulfatase effectively.822 The absolute configuration of this dual inhibitor was established by vibrational and electronic circular dichroism spectra analysis.823 A few years ago an overview (∼50 references) of DASIs was published bringing together all the known compounds that can as single agents exerting this important dual role.824 A series of naphthyltriazole-based derivatives 341 (R1 = Cl, Br and R2 = NH2SO2O−) turn outs to provide the best steroidal sulfatase inhibitor in the chloro compound and the most potent aromatase inhibitor in the bromo compound.825 The biphenyltriazole series 342 also produced some effective DASIs. Thus,

Sodium thiolate salts of a number of unprotected 1-thio sugars react with the β carbon of the sulfamate to give the corresponding S-linked amino acid glycoconjugates.830 The same group broadened the work later to include cyclic sulfamates from allo-L-threonine leading to threonine-glycosyl amino acids with good diastereoselectivity ≥ 97%.618 Some reactions of cyclic sulfamates derived from (R)- and (S)-serine, threonine, allothreonine, and α-methyl serine have been highlighted.831 The lengthy synthesis of a new, nonsulfamate anticancer drug, RCAI-36, modeled on the anticancer drug KRN7000, which is made by modification of the structures of agelasphins from the Okinawan marine sponge Agelas mauritianus, starts with reaction of the cyclic sulfamate 347 and the carbasugar 348.832 Synthesis of spiro-sulfamate glycosides 349 from exo-glycals through the agency of the Burgess reagents Et3N+SO2N−CO2R (R = Me, tBu) has been reported.833 Ring opening of enantiopure N-9-(9-phenylfluorenyl)serine-derived cyclic sulfamates 350 with β-keto-esters and -ketones and dimethyl malonate gave γ-substituted amino acid analogs, 351, in racemic form.834

342 (R1 = NH2SO2O−, R2 = H) showed exceptional potency in JEG-3 cells, and compound 342 (R1 = NH2SO2O; R2 = Cl) was also excellent.826 By combining the core motifs of two successful DASIs, two highly active dual inhibitors 343 (R1 = NH2SO2O−, R2 = Cl, Br) have been synthesized, and both show inhibitory activity at the picomolar levels for both aromatase and sulfatase inhibition.827 AM


Chemical Reviews

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5.4.2. Nucleoside and Nucleotide Sulfamates. A number of antiviral agents which are nucleoside sulfamates have been

Cyclic sulfamate 350 with R = tBu reacts with nucleophiles such as 1-imidazolyl−, PhS−, PhO−, −NCS, etc.) to give enantiopure (97% ee) tert-butyl γ-substituted α-aminobutanoate, Nu(CH2)2−CH(NH-9-Ph-9-FL)CO2tBu.835 The Lubell group examined the scope and limitations of the use of these N-(9-Ph-9-FL)serine-derived cyclic sulfamates for synthesis of amino acid derivatives. Two different mechanisms, i.e., nucleophilic displacement and β-elimination followed by Michael addition, were recognized for ring opening of the cyclic sulfamates.836 Ring opening of the homoserine-derived cumyl cyclic sulfamate, 352, with a series of amino esters and then selective cumyl ester removal giving dipeptidyl lactams has been carried out.837

reported. The 5′-O-[N-(aminoacyl)sulfamoyl]nucleosides 355 (R1 = Boc-L-Ser, Boc-L-Ser(Bz); R2 = H, CMe2) and some of these uridine derivatives showed high antiherpes simplex virus type 2 (HSV-2) activity.842 The guanosine analog 356 has been prepared in examining the antiviral activities of a series of derivatives, and 356 turned out to be inactive in vivo against Semliki Forest virus.843 The same group patented a series of 5′-sulfamoyl nucleosides as antiparasitics.844 Production of the antibiotic 5′-O-sulfamoyltubercidin 357 by biological means has been described. Compound 357 is an insectide and an acaricide, i.e., capable of killing members of the Acari group such as ticks and mites.845 The herbicidal nucleoside

Scheme 27. Synthesis of 5-O-Sulfamoyl Nucleosides

N-Alkylation of N-silyl peptides with five-membered 353 and six-membered 354 cyclic sulfamates minimized bis-alkylation and gave N-alkylpeptides.838 Ten lactam-bridged analogs of the growth hormone secretagogue GHRP-6 were synthesized using (S)-353 and (S)-354.839 Both (R)- and (S)-cyclic sulfamates derived from L- and D-aspartic acid were used to synthesize 12 βamino γ-lactam peptides using a well-established Fmoc protocol.840

2-chloro-5′-O-sulfamoyl adenosine 358 has been synthesized by two new and direct routes, and a number of derivatives were prepared.846 The sulfamoylated ribose derivative 359 has been prepared and then used in conjunction with other heterocycles to prepare a series of natural and unnatural 5-O-sulfamoyl nucleosides (Scheme 27).847 A novel chlorine-containing antibiotic nucleoside sulfamate 360 (R = H), known as AT-265, was isolated from Streptomyces rishiriensis, and its structure and biological properties were determined.848 A few years later AT-265 was again isolated and its structure confirmed as 360 (R = H), and it was named dealanylascamycin, and in the same study a second antibiotic 360 (R = NH2CHMeCO−) called ascamycin, which can be regarded as an N-acylsulfamate, was also isolated from a Streptomyces fermentation broth.849 The adenosine sulfamate MLN4924 361 was identified as a selective, mechanism-based inhibitor of NEDD8-MLN4924 adduct, and the related analog 362 is also reported in connection

Dimethylbiguanide reacts with sulfamic acid to give 90% of Me2NC(:NH)NHC(:NH)NH2·H2NSO2OH, which is used as an antidiabetic agent and displayed greater activity than dimethylbiguanide alone.841 AN


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with a mechanistic study of substrate-assisted ubiquitinactivating enzyme by adenosine sulfamate.850 The nucleoside sulfamates 363 (R = Me, Boc) have been prepared by reaction of the Burgess reagent Et3+NSO2N−Boc with suitable pyrimidine nucleosides.851 The first series of 5′-sulfamoylated carbocyclic purinyl nucleosides 364 (X = N, CH) has been synthesized and showed ID50 values as low as 62 and 15 nM, respectively.852 In subsequent work these researchers made other similar compounds such as 365 and found that they have antitumor and anti-HIV activities.853 Glycosyl-oxycarbonylsulfamate analogs of 3′-deoxythymidine and 2′,3′-dideoxyuridine have been

A novel synthetic route using p-nitrophenyl chlorosulfate, pNO2C6H4OSO2Cl, has been developed giving 3′-N-sulfamatemodified dinucleotides such as 368 which couple easily with alcohol or amine functionalities of other nucleosides.857 The method can also be used to introduce a sulfamide group. The sulfamate nucleotide analog, ribavirin 5′-sulfamate 369, inhibits Semliki Forest virus cytopathology by 50% at 10 mM, while ribavirin was active at 1 mM.858 Antiviral sulfamate-linked deoxyoligoribonucleotide analogs have been prepared.859

5.4.3. Inhibitors, Agonists, Natural Products, Etc. To probe the inhibition of HIV-integrase enzyme some N,Ndimethylsulfamates typically 370 gave the best cell-based antiviral activity with EC50 = 7 nM.860 Highly selective and potent sulfamate inhibitors of HPTPβ such as 371 were obtained

synthesized by reaction of 2,3,4,6-tetra-O-benzoyl-α-D-glucopyranose using chlorosulfonyl isocyanate and the corresponding 2′,3′-dideoxynucleoside.854 Replacement of the phosphorodiester linkage in oligonucleotides with sulfamate in order to increase lipophilicity and provide nuclease resistance has led to synthesis of several oligonucleotides with a sulfamate linkage typically of type 366 which can anneal to form stable duplexes which are resistant to cleavage by EcoR1 and snake venom phosphodiesterase.418 Substrate analogs of aminoacyl sulfamoyl adenosine have been shown to be inhibitors of adenylating domains of nonribosomal peptide synthetases.855 Replacement of the phosphodiester linkages in DNA with 3′N-sulfamate to give 367 (X = O) has little effect on the binding affinity for complementary DNA or RNA; however, replacement with a sulfamide moiety to give 367 (X = NH) results in destabilization of isosequential duplexes.856

by coupling a sulfamic acid phosphotyrosine mimetic with a malonate. The most potent had X = 3- or 4-NHSO3H with IC50 values of 0.10 and 0.06 μM, respectively.861 1,2,3,4-Tetrahydroisoquinolinyl sulfamic acids 372 (R = −CH2OPh, −(CH2)4Ph, −(CH2)2CO2H, −NHCH2Ph, etc.) AO


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are promising as phosphatase PTP1B inhibitors and have been synthesized in seven steps starting from tetrahydroisoquinoline3-carboxylic acid.862 Sulfamate 373 acts as an E1-activating enzyme inhibitor, particularly for NEDD8-activating enzyme, NAE.863 Another NAE inhibitor MLN4924 also contains a sulfamate group as seen previously,850 and two isotopically labeled isomers have been made. The first contains carbon-14 as shown in 374

GABAA (gamma-aminobutyric acid subtype) receptor activity for the sulfamate synthetic analogs 379 (R1,R2 = H,HO; Bn,HO; H,F) has been assessed, and 379 (R1, R2 = H, F) was inactive, but the other two sulfamates did show activity.872 A strategy for synthesis of FR900482 and the related mitomycins has been developed by the Trost group, and it involves nitrene insertion into a C−H bond using the rhodium catalyst Rh2(esp)2, giving the 10-membered cyclic sulfamate 380.873

6. SULFAMIDES 6.1. X-ray Studies

Crystal structure analyses of sulfamide and perdeuterated sulfamide have been reported, and evolution of the crystal structure between ambient temperature and the melting point at 363.5 K has been reported.874 Single-crystal X-ray diffraction of the CA isozyme IX inhibitor 4,6-diacetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranosyl sulfamide has been examined.875 The crystal structure of the boron-containing sulfamide 381 as an adduct with hCA II shows that its organic scaffold is bound to the hydrophilic half of the active site with many van der Waals bonds with IIe91, Gln92, Val121, Phe131, Leu198, and Thr200.876 The X-ray crystal structure of N-hydroxysulfamide, HONHSO2NH2, bound to hCA II has also been determined. The sulfamide inhibitor coordinates to the zinc active site involving a large number of hydrogen bonds with Thr199 and Thr200 and two water molecules.877 Crystal structures have been reported for a number of disubstituted sulfamides. Crystal structures for several N,N′dibenzylsulfamides, (p-XC6H4CH2NH)2SO2, have been determined. Assembly of these types of molecules leads to chiral twodimensional layers that also assemble into 3-D polar crystals with hydrogen bonding playing a key role in the sulfamide network with the benzyls above and below.878 This study has been extended using a series of additional N,N′dialkylsulfamides.879 The crystal structure of the sulfamide (dim-F3CC6H3NH)2SO2 has been determined.880 Crystal structures of the trisubstituted sulfamides, Me(MeSO2)NSO2NH(CO)N(MeSO2)Me,881 BnNHSO2N(CH2CH2Br)Bn,882 and BnNHSO2N(CH2CH2Cl)Bn,883 have also been published. Details of the crystal structures of two tetrasubstituted sulfamides have been reported. The tetrasubstituted sulfamides, [Et(p-NH 2 C 6 H 4 N)] 2 SO 2 884 and tBuOCO(CH 2 CH 2 Cl)NSO2N(CH2CH2Cl)2,885 have had their X-ray crystal structures determined.

synthesized in eight steps from the radioactive thiourea NH2(14CS)NH2, and the second is D8-MLN4924 in which the Indane ring is fully deuterated, which was synthesized in seven steps from d9-3-phenylpropanoic acid.864 Synthesis of sodium sulfamate salts with a phenylpiperazine structure incorporated 375 has been carried out, and they are inhibitors of human cytoplasmic protein tyrosine phosphatases.865 Synthesis of sodium and ammonium sulfamate salts of 2-(4aminophenyl)benzothiazoles, 4-(2-thiazolyl)-2-RC6H4NHSO2OM, has been done, and they have been assessed in vitro with human tumor cell lines.866 Cyclic sulfamates of type 376 prepared by copper- or rhodiumcatalyzed intramolecular aziridination from o-alkenylarenesulfonamides are active as calcium-sensing receptor agonists.867 Two new unusual steroidal sulfamates have been isolated from sponges found in the Philippines. Known as haplosamates they can inhibit HIV-1 integrase with IC50 values of ∼50 and 15 μg/ mL. The structure of one from an unidentified haplosclerid sponge is shown in 377.868 Total synthesis of (−)-muraymycin D2 and its epimer has been reported by a Japanese group.869 More recently the same group synthesized the cyclic guanidine amino acid L-epi-capreomycidine (Cpm) portion of muraymycin again via C−H nitrene insertion in a noncyclic sulfamate to give the desired cyclic sulfamate.870 Some 4′-modified noraristeromycins (NAM) including several sulfamates 378 (R1 = R3 = H, R2 = NH2SO2O−; R1 =

6.2. Computational, Spectroscopic, and Magnetic Studies

An ab initio study of the conformation and electronic properties of sulfamide has been reported. The lowest energy conformation was found for a cis−trans amino group arrangement. The most polar conformation has dihedral angles of 180° and has the largest dipole moment (∼6.6 D), well beyond that of the other conformers.886 Semiempirical (PM3) and ab initio MO and local density function methods (LDF) have been used to calculate geometric and electronic properties for 22 sulfur compounds including one nitrogen−sulfur compound, namely, sulfamide.887 Calculations at the MP2 level gave the dipole moment of sulfamide as 4.39, in reasonable agreement with the experimental value of 3.9. A report on the X-ray structure of 4,6-diacetyl-2,3-dideoxy-α-Derythro-hex-2-enopyranosyl sulfamide was noted above,875 and

H, R2 = NH2SO2O−, R3 = NH2; R1 = NH2SO2O−, R2 = R3 = H; R1 = NH2SO2O−, R2 = H, R3 = NH2) have been made and their inhibitory activities against Plasmodium falciparum and human Sadenosyl-L-homocysteine assessed.871 AP


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the same workers very recently reported a theoretical and spectroscopic study of this novel glycosyl CA IX inhibitor. The αanomeric form is more stable than the β form with solvent effects included, and calculated NMR shift data support findings regarding configuration and conformation assignments of this sulfamide888 Theoretical methods have been used to examine some other sulfamides also. Geometry optimization techniques and transition state (TS) detection at the B3LYP/6-31G** level indicate that for synthesis of symmetric N,N′-substituted sulfamides the “direct route” rather than a pyridine-assisted route is favorable.889 Seventeen sulfamides made up of mono-, di-, tri-, and tetrasubstituted compounds have been synthesized and assessed as possible anticonvulsant agents. Sulfamides (nPrNH)2SO2 and nBuNHSO2NH2 performed well in the two standard tests, namely, the MES and the PTZ tests.890 A 3dimensional SAR for 27 known potent anticonvulsants (correlation coefficient r2 = 0.967) using comparative field analysis (CoMFA) gave a 3D-QSAR for predicting the activity of new antiepileptic compounds including sulfamides.891 Complexation of N-nitroso-N′-2-chloroethyl-N′-piperidinyl sulfamide with β-cyclodextrin has been examined using DFT. The computed structure for the complex is in good agreement with MS and nitrogen-15 NMR.892 Raman spectra of powdered sulfamide have been recorded at 300 and 77 K in the 4000−50 cm−1 range with special attention to the low-frequency region where no literature data are available.893 The same group looked at the IR and Raman spectra over the 4000−100 cm−1 range of polyethylene oxide−sulfamide complexes of general formula P(EO)nNH2SO2NH2 (n is the ratio of monomer units per sulfamide molecule and varies from 2 to 30).894 Raman spectra of tetraethyleneglycol dimethylether (TEGDME) and sulfamide were recorded at 300 K over the range 4000−100 cm−1.895 A review (∼77 references) appeared in 1997 as a feature article of the chemical and physical properties of sulfamide.896 An ESR study of the radical cation of N,N′-tetramethylsulfamide, (Me2N)2SO2 •+ in solid CFCl3 at 77 K has been reported, and its photofragmentation has been observed. The dimethylamine radical cation formed [MeNH•+] when it was irradiated with red light at λ > 570 nm.897 The same group also reported an EPR spectroscopic and theoretical study of tetraalkylsulfamides, (Me2N)2−, (Et2N)2−, (Me2CHN)2−, [(cyc-C6H11)2N)2]−, [(C4H8ON)]2−, and [(C5H10N)2]−SO2. Photofragmentation on irradiation again takes place to give various secondary radicals.898

A novel basic proton-conducting polymer (proton-vacancyconducting polymer) based on PEO (poly(ethylene oxide)), sulfamide, and a doping agent such as guanidine carbonate, (H2NC(NH)NH2)2·H2CO3, has been made. The phase diagram for P(EO)nNH2SO2NH2 (n is the ratio of monomer units per sulfamide molecule) showed three eutectics and three intermediate crystalline compounds.901 A similar type of polymer with sulfamide and poly(methylmethacrylate) and side oligo(oxyethylene) chains of variable length has also been made by the same group. The various complexes were investigated by differential scanning calorimetry (DSC) and ac impedance techniques.902 N,N′-Diaryl(and dialkyl)sulfamides and sulfamide polymers can be prepared directly from sulfur dioxide. A ∼100fold excess of SO2 with I2 and pyridine or Et3N in ACN converted smoothly and rapidly aromatic amines into N,N′-diarylsulfamides in yields of 20−87%. The Et3N/SO2/I2 mix generally provided better yields than the pyridine/SO2/I2 system, and they can be improved using DMAP or quinuclidine. PolyalkylsulfaScheme 28. Synthesis of N-Alkylsulfamates by Ring Opening of Catechol Sulfate

mides such as 382 could be produced in 35% yield using this methodology starting from p-phenylenediamine, sulfamide, and an ice-cold solution of Et3N in ACN saturated with SO2 and I2 added after.903 Analysis of sulfamide by volumetric determination of nitrogen gas liberated after treatment with sodium hypobromite NaBrO can be carried out quickly and the relative error is ±1.0%.904,905 Analysis of volatile impurities from the rodenticide tetramethylenedisulfotetramine (TETS or tetramine) has been carried out by reaction with sulfamide, giving 383 and TFA or HCl using two-dimensional GS-MS.906

6.3. Inorganic, Industrial, and Analytical Studies

Industrial synthesis of sulfamide from ammonia and sulfuryl chloride at −5 °C giving a 30−40% yield has been described.899 Sulfamide dye intermediates of type 2-NO2 and 5- or 6R1C6H3NHSO2NR2R3 (R1 = H, halo, alkyl, alkoxy; R2, R3 = H,

7. ALICYCLIC SULFAMIDES 7.1. Synthesis

7.1.1. Mono- and Disubstituted. Two papers deal with preparation of the parent compound sulfamide. Sulfuryl chloride reacting with hexamethyldisilazane at 30−40 °C gives N,N′-bistrimethylsilylsulfamide, which can after workup be precipitated out of solution.907 Ammonium nitrate reacted with gaseous ammonia to give a solution which on subsequent treatment with SO2Cl2 gave 53−59% yields of sulfamide.908 An unusual but high-yielding route (85−88%) to the Nalkylsulfamides 384 has been reported. It starts with ring opening of catechol sulfate followed by reaction with the amine, whose R group is to be included in the final product, giving 384 (R = Bn, Ph(CH2)2−, 3-PhnPr−).909 Sixteen sulfamides of general type Me(CH2)12NHSO2NHR (R = H, nPr) with chains having up to 20 carbons and containing between one and four CC double

alkyl, cycloalkyl, aryl, heteroaryl; R2, R3 = heterocycle) have been prepared from the corresponding sulfamoyl chloride and R2R3NH at −30−100 °C in tertiary amine base.900 AQ


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Probably the first known sweet-tasting sulfamide was reported over 20 years ago by Unterhalt (when R = NO2, CN and n = 1) in

bonds have been prepared, and they displayed modest cannabinoid properties in binding assays.910 Monosulfamides of type 303 with the C-17 sulfamate group replaced with −NHSO2NH2 have been reported recently.772 Recently, another unusual synthesis of mono- and N,Ndisubstituted sulfamides with sulfamoyl chloride involves preparation of the sulfamoyl chloride RO(CO)NHSO2Cl with chlorosulfonylisocyanate and ROH followed by reaction with R1R2NH giving an intermediate which hydrolyzes to NH2SO2NR1R2. The example given involves formation of benzylsulfamide.911 It would be interesting to know how general this synthesis might be. Monosubstituted and more highly substituted sulfamides from reaction of alcohols with oxycarbonylsulfamide compounds, R1R2NSO2NH(CO)OR3, have been reported. Up to 90% benzylsulfamide was prepared by this method.912 An important method for preparing disubstituted sulfamides and sulfamide polymers was discussed above.903 Synthesis of the N,N′-disubstituted sulfamide, (o-,m-di-CF3C6H3NH)2SO2, from 3,5-ditrifluoromethylaniline and SO2Cl2 with NEt3 in CH2Cl2 in 35% yield has been described.880

p-RC6H4NHSO2NH(CH2)nCO2H; the compounds had approximately the same degree of sweetness as cyclamate, but when R = NO2 and n = 2 there was a strong bitter aftertaste.917 DABCO + SO2 = DABSO (i.e., DABCO-bis(SO2)), and this bench-stable colorless solid is suitable for organic synthesis replacing SO2 gas. Its reaction with anilines and iodine leads to formation of sulfamides RC6H4NHSO2NHC6H4R (R = H, p-Br, p-MeO, p-Me, o-Me, and RC6H4 = 2,4,6-triMeC6H2) in about 65% yields.918 Reaction of 387 (R = H) with CCl3CSCl gave 387 (with R = CSCCl3 and R1,R2 = (cyclo)alkyl, aryl; NR1R2 = heterocyclo).919 New chiral sulfohydantoins 388 have been made starting from symmetrical sulfamide derivatives of natural amino acids as aglycones.920 The N,N-disubstituted sulfamide 389 is an intermediate en route to doripenam, the broad spectrum βlactam antibiotic.921 The unusual sulfamide N,N′-bis(1-trishomobarrelenyl) sulfamide, 390, which was obtained in 84%, is

Amination of o-NO2C6H4NHSO2Cl with R1R2NH (R1 = H, Me, Et, R 2 = Ph; R 1 = R 2 = Et; R 1 R 2 = (CH 2 ) 5 −, −(CH2)2O(CH2) 2) gave 37−85% of the corresponding sulfamide.913 N-Alkyl-N′-(1-carboalkoxyalkyl)sulfamides, such as BnNHSO2NHCH2CO2But, were prepared by treating sulfamates of type BnNHSO2OC6H4OH-o with amino acid alkyl esters such as glycine tert-butyl ester.914 Reaction of (BnRN)2SO2 (R = Bn, 2-phenylethyl, 3phenylpropyl) with sodium in ethylenediamine gave the corresponding sulfamide (RNH)2SO2.915

involved in the synthetic route to 1,1′-bis(trishomobarrelenyl).922 Another unusual sulfamide N,N-bis(bicyclo[1.1.1]pentyl)sulfamide, 391, is a precursor in the synthesis of the smallest bicycle azo compound, namely, bisbicyclo[1.1.1]pentyldiazene.923 A number of papers have come out on preparation of the ulcer inhibitor famotidine, 392, and intermediates to it. Compound 392 can be made from thiazolylmethyl(thio)propionimidates 393 (R1 = alkoxyethyl, hydroxyethyl). Thus, 393 (R1 = −CH2CH2OEt) reacted with thiourea in MeOH over 2 days to give 64% yield.924 Four papers have dealt with preparation of the intermediate propionamidine derivatives, and in each case sulfamide925 or sulfamide derivatives926−928 are involved. The N,N′-disubstituted sulfamides, RNHSO2NHR (R = iBu, Bn, NH2CO(CH2)2−, NH2CO(CH2)3−, pMeOC6H4(CH2)2−, and PhCHMeCH2−) have been used to design a previously unrecognized 2D structural motif for selfassembly of 3D molecular arrays.929 The same group developed a chiral packing motif based on N,N′-bis(4-substitutedbenzyl)sulfamides, (p-XC6H4CH2NH)2SO2 (X = H, MeO−, F, Cl, Br, Me, and −CO2Me); chiral 2D layers that evolve into 3D polar crystals are formed.878

Several N,N-disubstituted sulfamides are involved in the synthesis of the sulfamoylurea hypoglycemic agent Gliamilide, which has a trisubstituted sulfamide as part of its structure. These trisubstituted sulfamides all incorporate the structural feature shown in 386.916 AR


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Scheme 29. High-Yield Synthesis of Sulfamides from N,N′Disulfurylimidazole

arylsulfamides involves treatment of cyclic urethanes 397 (Q = (CR6R7)n, n = 0, 1) with amines.937 Eighteen hydrazinesulfamides such as MeNHSO2NH−NHR and PhCHNN(Me)SO2NMe2 have been reported.938 Synthesis of the tetrasulfamides, 2-chloroethylnitrososulfamides, R1R2NSO2N(NO)CH2CH2Cl, known as (CENS), was achieved by reacting chlorosulfonylisocyanate and oxazolidinones 398. Aminolysis of 398 gave rise to N-carbamoylsulfamides such as BnNHCO2(CH2)2NHSO2NH(CH2)2Cl.939 A transsulfamoylation procedure using denitroso-CENS and

Co-condensation of aldehydes and MeNHSO2NHMe with Lewis acid catalysts leads to ∼50% yields of cyclic dihydropyrimidone products.930 Sulfamide-linked dinucleosides with both pyrimidine and purine bases 394 (B = T, R1 = DMTr, R2 = TBDMS; B = T, R1 = DMTr, R2 = H) have been synthesized. Conformational analysis showed that replacing the phosphodiester link results in a shift from a mainly southern (C2′-endo) to a northern (C3′-endo) ribose ring conformation.931,932 7.1.2. Tri- and Tetrasubstituted. Some papers have dealt with synthesis of tri- and tetrasubstituted sulfamides. Reaction of Me2NH and SO2Cl2 and an appropriate aniline gave the

amines R3R4NH gave products R3R4NSO2N(NO)CH2CH2Cl in 75−80%.940,941 An X-ray crystal structure of a CENS Scheme 30. Copper(II)-Catalyzed Preparation of Bicyclic Ring Sulfamides from N,N′-Disubstituted Sulfamides

compound showed a strong structural analogy to a closely related nitrosochloroethylurea.942 7.1.3. Metal Catalyzed. Palladium-catalyzed reaction of sulfamide with PhX (X = Cl, Br, I, and OTf) with Pd2(dba)3 induces Hartwig−Buchwald coupling to give arylsulfamides PhNHSO2NH2 in yields varying from 10% to 73%. The coupling/arylation reaction can be extended to include preparation of sulfamides ArNHSO2NH2 (Ar = 1-naphthyl, pCl, and p-MeO-C6H4) in yields of 61−79%.943 This reaction has also been carried out with R1R2NSO2NH2, the same Pd catalyst, and aryl halides to give R1R2NSO2NHAr (R1,R2 = alkyl, benzyl, and aryl; Ar = aryl, heteroaryl). More than 20 reactions work well, and a wide range of functional groups can be tolerated.944 Zinc- a nd indium-mediated allylation of N,N (dimethylsulfamoyl)benzaldimine with allyl bromide in various solvents at room temperature gives yields of 13−90% of sulfamide 399. Use of other bromides (crotyl, methallyl, prenyl) leads to good yields of other substituted sulfamides.945 This reaction has been revisited, this time employing a Pd complex-catalyzed allylation of N,N-dimethylsulfamoyl-protected aldimines in DMF with allyl(tributyl)stannane leading to preparation of N-homoallylic sulfamides such as 399, again with excellent yields from 60% to 96%.946 The tetrasubstituted aziridine−sulfamides 400 have been prepared by reaction of Ph−CHNSO2NMe2 with the sulfonium salts 401, giving yields of 57−77% in the presence of lithium tert-butoxide.947 The first palladium(II)-catalyzed intramolecular amino-bromination and -chlorination of olefins such as 402 in the presence of a stoichiometric amount of

trisubstituted sulfamide o-,p-R(NO2)C6H3NHSO2NMe2 (R = F, Cl, Br, and CF3).933 A variety of sulfamides, including sterically hindered and electronically deactivated, has been prepared using a methodology that starts with N,N′-disulfuryldiimidazole which is alkylated and then reacted with amine followed by a second alkylation and reaction with another amine to give tetrasubstituted substituted sulfamides (Scheme 29). About 35 tri- and tetrasubstituted sulfamides have been made in excellent yields using this method.934 Some bisaziridine sulfamides 395 (R = Bn, iPr, and iBu) have been prepared in ∼90% yields starting from N,N′-[(NHCH2(R)CO2Me)]2SO2.935 Certain types of tetraarylsulfamides can be prepared generally in ≥70% yields by reaction of arylsulfamoyl imidazolium triflates such as 396, which are readily prepared from the corresponding chlorides with amines. One of the arylsulfamides made by this method is a bioisostere of the drug muraglitazar, which is in clinical development for treating type 2 diabetes and dyslipidemia.936 Another route to multisubstituted AS


Chemical Reviews

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405, is a key intermediate in the route to 1,2,5- and 1,2,4-

copper(II) halide and Pd(OCOCF3)2 in THF led to synthesis of several bicyclic open-chain sulfamides like 403.948 The copper(II)-promoted doubly intramolecular alkene deamination (Scheme 30) converts the open-chain N,N′disubstituted sulfamide to a bicyclic ring sulfamide using copper(II) diacetate in DMF and DMSO at 90−120 °C over 48 h. The scope of the reaction can be extended considerably using copper(II) neodecanoate in place of acetate.949 A review (∼146 references) of recent progress in transitionmetal-catalyzed hydrofunctionalization of less activated olefins

imidazoles.956 Introduction of the iodo and thiophenyl groups onto 405 is achieved in two steps. N-Hydroxysulfamides R1NHSO2N(OH)R2 (R1 = H, R2 = Bn, cyc-hexyl; R1 = Et, ptBuC6H4, R2 = Me) have been prepared in 85−97% yields by hydrolysis of sulfamides Boc-NHSO2N(R)-OTBDMS .957

7.2. Reactions

7.2.1. Metal Catalyzed. Reaction of triethylsilyl chloride, sbutyllithium, and 1-(N,N-dimethylsulfamoyl)imidazole 405 in DMF gave the imidazolesulfamido derivative 406.958 Reaction of ClPh 2 P:NSO 2 Cl with ammonia gives NH2SO2N:PPh2NH2, which can be converted to Me3Si(H)NSO2N:PPh2N(H)SiMe3 with Me3SiNMe2, and this reacts with WOCl4, giving the remarkable eight-membered ring system 407 whose structure was confirmed by X-ray crystallography.959 The rhodium/phosphoramidite-catalyzed asymmetric arylation of N,N-dimethylsulfamoyl-protected aldimines Ar1CH NSO2NMe2 (Ar1 = p-XC6H4-, X = Cl, F, CF3, MeO, and Me) has been carried out using the catalyst Rh(acac)(CH2CH2)2 together with various phosphoramidite catalysts and the arylboron compounds Ar2B(OH)2 (Ar2Ph, p-XC6H4, X = MeO, Me) giving 408 in very good yields. Removal of the

has some examples involving both alicyclic and cyclic sulfamides.950 7.1.4. Use of Boc and Other Reagents. Moderate yields of various unsymmetrically substituted sulfamides have been

achieved using solid-phase bound amines and the sulfamoylating agent >N+C6H4NSO2N−CO2But giving polymer bound Boc sulfamides which can be deprotected and cleaved to give free sulfamides.951 A similar type of reagent with chlorosulfonylisocyanate gives in a one-pot synthesis N-(tert-butoxycarbonyl)sulfamide, tBuOCONHSO2NH2, in 96% yield via a pyridinium salt.952 Removing the Boc protecting group from sulfamides can be done using silica−benzenesulfonic acid and microwave heating. 953 In this work a number of Boc-protected (tetrasubstituted)sulfamides were also prepared in reasonable yields using microwave heating. Using the reagent Nsulfamoylcarbonimidate (PhO)2CNSO2NH2, prepared from sulfamide and dichlorodiphenoxymethane, and amines R1R2NH compounds R1R2N(PhO)CNSO2NH2 have been prepared, and replacement of the second phenoxy group occurs with NH3 in refluxing iPrOH giving the guanidines, R1R2N(NH2)C NSO2NH2.954 This paper illustrates how the sulfamoyl carbonimidate can be used to introduce the sulfamide moiety into a number of heterocyclic compounds.

dimethylsulfamoyl protecting group gives ready access to important asymmetric diarylmethylamines.960 Scheme 31. Cyclization of Open-Chain Sulfamides to Substituted Isoquinolines

In related work some years later the rhodium catalyst [RhCl(CH2CH2]2 has been employed to effect the asymmetric additions of arylboron nucleophiles ((PhBO)3, (pClC6H4BO)3, [PhBF3]K, etc.) to PhCHNSO2NCHPh, giving diarylated sulfamides 409 with extremely high enantioselectivities and good to excellent diastereoselectivities.961 Use of nickel(II) salts as catalysts to effect homogeneous oxidation of alkenes (direct diamination) has been achieved using the sulfamide CH2 CHCH2CPh2CH2NHSO2NHCO2Me and NiCl2·6H 2O in DMF at 25 °C giving a 71% yield of 410. Bipyridylnickel chloride gave an 80% yield of 410 at 40 °C in a shorter reaction time.962

N,N′-Disubstituted unsymmetrical sulfamides R1R2NSO2NR3R4 can easily be prepared by reaction of Nsubstituted oxazolidin-2-one derivatives 404 with secondary amines R3R4NH giving yields of 62−87%.955 The dimethylsulfamoylated imidazole, 1-(N,N-dimethylsulfamoyl)-1H-imidazole, AT


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Scheme 32. Reaction of 1,1′-Sulfonylbis(benzotriazole) with Secondary Amines

Scheme 33. Kinetic Study of the Cyclization of Open-Chain to Cyclic Sulfamides

antidepressant drug citalopram.971 Chiral bifunctional sulfamides such as 419 are efficient catalysts for conjugate addition of ketones to nitroalkanes. Addition of acetone to the βarylnitroethylenes Ph−CHCHNO2 gave generally good yields of 420 with reasonable enantioselectivities.972 Chiral pyrrolidinyl sulfamides are another class of bifunctional catalyst, for example, 421, which can act as a catalyst for direct asymmetric Michael addition of cyclohexanone to nitroalkenes, ArCHCHNO2, to give 422 with % ee ≈ 80+.973 New nitrogen−phosphorus bonds form in the reaction of sulfamides NH2SO2Y (Y = BuNH, Me2N) with di(P2O74−) and

Pd(0)-catalyzed allylation of sulfamide with allylic carbonates R1CHCHR2CH2OCO2Et gave a number of mono-, di-, tri-, and tetrasubstituted sulfamides.963 In an accompanying paper the same group reacted sulfamide under similar conditions with

tri(P3O105−) phosphates giving compounds such as the amidodiphosphates BuNH−P2O63− and NH2−P2O63−.974,975 Another type of nitrogen−phosphorus compound forms when the phosphoroamidates, (EtO)2P(O)NHR, react with SO2Cl2 in dichloromethane giving N,N′-bis(diethylphosphoryl) sulfamide, (EtO)2P(O)NHSO2NHP(O)(EtO)2. Reaction of phosphoramidates with SO3 in CCl4 at −20 to −15 °C gave the diethylphosphoryl sulfamide, and there was evidence for formation of the phosphorus sulfonylamine, (EtO)2P(O)

the bis-carbonate EtOCO2CH2C(CH2)CH2OCO2Et giving 68% of 411.964 Various reactions of the sulfamides 412 (R = H, N3, Br, and BnNH) catalyzed by MeLi, Pd/C, SmI 2 , and tris(dibenzylideneacetone)dipalladium(0) chloroform adduct, Pd2(dba)3·CHCl3, have been examined.965 Reaction of 1Hindole-3-carboxaldehyde and sulfamide with platinum oxide catalyst yields the anticancer agent 5,6,11,12,17,18,23,24́ octahydrocyclododeca[1,2-b:4,5-b′:7,8-b′:10,11-b′]tetraindole (CTet).966 7.2.2. Other Reactions. Sulfamides 413 (n = 1, 2, 3) have been reported in 66%, 73%, and 80% yields for n = 3, 2, and 1, respectively, on reaction of sulfamide with suitable acetals.967 Alkylation of N-Boc-N′-(2-chloroethyl)sulfamide, BocNHSO2NH(CH2)2Cl, with electron-deficient alkyl bromides RBr and the Mitsunobu reagent gives moderate yields of the Nalkylated products. This method was also useful for the Nglycosylation of carbohydrates and proved to be anomerically selective.968 Open-chain sulfamides 414 cyclize to compounds 415 (Scheme 31) in the presence of ethyl chloro(methylthio)acetate and SnCl4 in refluxing 1,2-dichloroethane to give ∼70% yields. Products can be easily decarboxylated to give over 70% yields of R-substituted isoquinolines.969 Reaction of 1,1′-sulfonylbis(benzotriazole) 416 with secondary amines leads to varying amounts of products 417 and 418 (Scheme 32).970 5-Carboxyphthalide can be dehydrated in the presence of SOCl2 in sulfolane and in the presence of sulfamide to give 5cyanophthalide, an intermediate in the preparation of the

NSO2], and the elusive diethylphosphoryl sulfamic acid, (EtO)2P(O)NHSO3H.976 7.2.3. Mechanistic Studies. The kinetics and mechanism of the solvolysis (hydrolysis and methanolysis) of a series of Narylsulfamides, X,Y−C6H3N(R)SO2NH2 (R = H, Me; X,Y = variously H, Br, CO2Me), have been investigated. Both addition−elimination E1cB and general acid catalysis mechanisms have been observed depending on the substrate, and the effects of the ring substituents are reversed for each of these mechanisms.977 The kinetics and mechanism of cyclization of 423 (R = H, Me and iPr) to 424 in various amines (nBuNH2, NH2CH2CH2OH, C4 H9NO, NH2CH2CONH 2) in KOH solutions have been studied (Scheme 33). The cyclization displays both general base and general acid catalysis. With a Bronsted β of 0 the breaking off of the proton from a negatively charged tetrahedral intermediate is seen as the slow step of the reaction. Compound 424 (R = iPr) is the well-known herbicide Bentazon or Basagran.978−980 AU


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The ratio of the relative rate constants for the cyclization reactions of 425 (R1 = H, R2 = Me), 425 (R1 = Me, R2 = H), and 425 (R1 = R2 = H) are 1:20 000:100, and each reaction is subject to base catalysis with decomposition of a tetrahedral intermediate being the rate-determining step.981 The kinetics

inhibitor, and other analogs such as 427 (n = 4, 5) are also weak inhibitors.983

of decomposition of 2-chloroethylnitrososulfamide derivatives (CENS) R1R2NSO2N(NO)CH2CH2Cl (R1 = R2 = cyc-hexyl, Bn and R1R2NC5H10N) have been studied in aqueous buffered solutions with pH from 0 to 14, and the mechanism involves denitrosation of the substrate and competitive hydrolysis with nucleophilic attack on sulfur and formation of sulfamates.982

The affinity of sulfamides such as R1NHSO2NHR2 (R1 = R2 = nPr, C4H8NO, Ph(CH2)2, cyc-Pr-; R1 = H, R2 = nBu, cyc-hexyl, Bn) for CA II have been assessed by experimental and molecular modeling techniques. 667 In common with sulfamate,669 sulfamide shows inhibitory activity with two new β-CAs. Three CA isozymes hCA I, hCA II, and bCA IV have been used for assessing the inhibitory properties of sulfamides, such as 428 (R = CONHSO2NH2, CH2OCONHSO2NH2), and the latter acylated compound was found to be very potent as a CAI.675

7.3. Biological, Medicinal, Inhibition, and Other Uses

7.3.1. CA and Kinase Inhibitors. Two reviews cited earlier have important sections on the role of sulfamide derivatives as CA inhibitors.656,666 Using topiramate, 10, as a structural platform, Maryanoff and colleagues developed series of sulfamides, such as 426 (X = S, C), as CA II inhibitors,696 and they examined the thermodynamic binding properties for sulfamides with human CA II inhibition using the ThermoFluor method.680 The direct sulfamide analogue of topiramate, i.e., 10, with the side-chain −CH2O− replaced with −CH2NH− is a weak

A new series of benzylated and peracetylated glycosylsulfamides 429 (R = Bn, Ac) behaved as weak inhibitors of five human CA isoforms hCA I, II, IV, IX, and XII.984 Inhibition of CA AV


Chemical Reviews

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isoforms I−XV with the boron-containing sulfamide 381 and the crystal structure of the adduct of 381 and hCA II shows the organic scaffold bound in the hydrophilic half of the active site.876 A series of 2-substituted 1,3,4-thiadiazole-5-sulfamides 430 acts as a powerful and selective inhibitor of the mitochondrial isozymes VA and VB.985 Piperidinylsulfamides of types 431 and 432 have been patented as CAIs, and 432 had an IC50 value of 6.6 μM in

The cyclic sulfamide 446 is active against Norwalk virus, and using it as a scaffold a large number of related compounds have

vitro,986 and the same group patented compounds 433 and 434 with the former giving IC50 values from 6.5 to 7.3 μM.987 A QSAR has been established for a small set of CA-inhibiting sulfamides 435 (R = I, Br, CF3, CN, OH, CO2Et, and COPh) with a correlation coefficient (r) of 0.914.988 Sulfamides 436 and 437 selectively target cancer-associated CAs (IX and XII).989 A series of new monomethoxy isoquinoline sulfamides 438 showed better hCA inhibitory activity against several isoforms compared to the dimethoxy analogs.990 Some trisubstituted sulfamide derivatives 439 have been patented as mitogen-activated protein kinase (MEK) inhibitors,991 and some N-aryl-N′-alkyl sulfamides such as 440 have also been patented for the same purpose.377 Large-scale synthesis (2.71 kg in 7 steps) of the c-Met kinase inhibitor 441 has been developed.992 7.3.2. Protease Inhibitors. The synthesis and γ-secretase inhibitory activities of some bridged bicyclic sulfamide derivatives such as 442 and 443 have been described.993,994

been synthesized and tested leading to development of an SAR.999 Functionalization of the methyl ester of a protected Lornithine 447 with a sulfamido group produces compounds 448

that can be used to develop a new class of human thrombin inhibitors.1000 The sulfamide compounds 449 (n = 0, 1; R1 = R2 = H; R1 = Me, R2 = H; R1 = H, R2 = Me; R2 = H and R1 = nPr, Bn, Ph(CH2)2−) are novel TS analogue inhibitors for carboxypeptidase A (CPA). The parent compound (S)-449 (n = 0; R1 = R2 = H) displayed potent inhibitory activity, and its enantiomer was much less potent.1001 These authors also synthesized compounds 449 (n = 0, 1; R1 = OH, R2 = H; R1 = H; R2 = OH) as potential inhibitors for CPA and compared their inhibitory activity.1002 The sulfamido phenylcyclopropanecarboxylate 450 was the lead compound in development of a SAR, inhibiting the zinc metalloproteases aggrecanase-1 and -2. They are the major enzymes that cause aggrecan cleavage at the Glu373 and Ala374 sites.1003 7.3.3. Inhibition of Other Enzymes. A series of pyrazolopyridine sulfamide inhibitors 451 (R = −NHEt, −NHPri, −NMe2, −NHCH2CHF2, −N(Me)Et, N-pyrrolidyl) of B-RafV600E has been made and a SAR developed.1004 A number of sulfamides of type 452 have been patented as GlyT1 glycine transporter inhibitors. They are used in treatment of neurological and neuropsychiatric disorders.1005

Syntheses of sulfamide derivatives RN(iBu)SO2NHtBu, where R = NH 2 C(Bn)CH 2 (OH)CH 2 CH 2 − and BnCO(Me 2 )CONHC(Bn)CH(OH)CH2CH2−, as retroviral protease inhibitors have been patented.995 Some cyclic sulfamides 444 (R1 = Bn, OPh; R2 = MEM) have been synthesized, and their inhibitory potencies against HIV-1 protease were compared with calculated free energies of binding derived from molecular dynamics simulations.996 A crystal structure of 444 (with R1 = OPh and R2 = H) cocrystallized with HIV-1 protease showed an unexpected conformation in which the side chains were transposed.997 Some sulfamide and bis-sulfamide amino acid derivatives, for example, 445, are inhibitors of proteolytic enzymes.998 AW


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Potential inhibitors of the crucifer phytoalexin brassinin have been developed by replacing the dithiocarbamate group of

focused on lysine-derived sulfamides of type 459 as histone deacetylase inhibitors. Extensive change in the aromatic rings has been made including introduction of thiazole, imidazole, triazole, and oxadiazole rings in 459.1010 7.3.4. Protein Inhibitors. ATP-competitive kinesin spindle protein (KSP) inhibitors have been developed based on the brassinin 453 with various groups including sulfamide to give compounds ArCH2NRSO2NH2 (Ar = 1- and 2-naphthyl, 3indolyl, R = H, Me).1006

templates shown in 460 and 461. In 460 R1, R4 are generally H, R 2 = −NHSO2NH2 or −NHSO2NMe2 and R3 various substituents, and in 461 R1 = −NHSO2NH2, R2 = H, and R3 = m-F, m-NO2, m-NH2 p-CF3C6H3, and a series of benzofused dioxane/dioxoline rings. Compound 460 (R1, R3, and R4 all H, R2 = −NHSO2NH2) shows considerable promise as a potent KSP

Figure 3. Synthesis of sulfamide β3-adrenergic receptor agonists.

Sulfamides 454 have been synthesized as inhibitors of genotype 1 HCV polymerase, and some SARs have been found.378 The pyrazole-based sulfamides 455 are potent inhibitors of mammalian 15-lipoxygenase.1007 Some indoline-based sulfamide

Figure 4. Sulfamide-based NPYY5 receptor antagonists.

inhibitor with in vitro antiproliferative activity against human cells.1011 A number of quinazolin-4-piperidin-4-ethyl sulfamides 462 (n = 0, 1, 2 and R1 = MeO or H, R2 = H; n = 0, 1, 2, R1 = MeO, R2 = 3-pyridinylCHCH−) have been identified as PC-1 (NPP-1) inhibitors which should be useful in treatment of calcium

derivatives 456 have been synthesized and evaluated as novel acyl-CoA: cholesterol acyltransferase inhibitors.1008 Several different types of sulfamide typified by 457 (n = 4, 5, 6; R = H, Me, COMe) and 458 have been examined as histone deacetylase inhibitors.1009 Further work by the same group has AX


Chemical Reviews

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pyrophosphate dehydrate (CDDP) deposition disease and

Potent NPY5 antagonists based on the 5-(2′-pyridyl)-2aminothiazole scaffold exhibit high affinity at the NPY5 receptor, and a series of seven sulfamides 472 (RRN = Me2N, NH2, Et2N,

osteoarthritis.1012

Various piperidinylsulfamoyl chlorides 463 (R = −CO2Bn, −CO2Me, and −CO2(CH2)4Ph) have been reacted with a variety of amines in dichloromethane to yield generally 70−95% product sulfamides which are novel FKBP-12 inhibitors where the known ketoamide has been replaced with sulfamide.1013 A semisynthetic acylsulfamide 464 which inhibits Ub/Ubl E1activating enzymes has been designed and synthesized.1014 7.3.5. Agonists and Antagonists. A patent has described the synthesis of sulfamide β3-adrenergic receptor (AR) agonists, see Figure 3.1015 The same researchers made another series of sulfamide-based agonists 465 which are also effective as β3-AR agonists.1016 Oxazole-containing sulfamides such as 466 have been prepared as PPARα agonists.1017 Simple sulfamides such as R1NHSO2NHR2 with long chains which may contain double carbon−carbon bonds are active PPARα agonists. When R1 = octadecyl and R2 = nPr the sulfamide produced a marked effect in reducing body weight and blood triglycerides.1018

morpholino, 2,6-dimethylmorpholino, N-Me piperazino, and (MeO(CH2)2)2N) was effective.1024 Patents from a Japanese group1025,1026 have also developed sulfamide-based NPYY5 receptor antagonists as shown in Figure 4. 7.3.6. Benzo-Fused Heterocycles. A large number of patents and papers in this area deal mainly with neurological disorders. The benzothiophene sulfamides 473 have been patented for use in treatment of epilepsy and epileptogenesis,1027 and related benzofurans have also been patented for the same purpose.1028 Other ring systems in place of the benzothiophene system in 473 include the benzodioxin 4741029 and the benzodioxepin 475 systems.1030

Maryanoff examined 473 (JNJ-26990990) and closely related benzothiophene derivatives. Compound 473 showed excellent anticonvulsant activity in rodents and very weak human CA II

Three patents from the same group described some pyrimidine sulfamides that act as endothelin receptor antagonists.1019−1021 The sulfamide-containing compounds of types 467, 468, and 469 have been synthesized, and biological evaluation of each type as been carried out. Compounds such as 470 have been patented as integrin α4 antagonists for treatment of inflammatory and immune disorders.1022 A series of sulfonamides and sulfamides has been designed as cannabinoid receptor 1 (CB1) antagonists, the latter based on the template shown in 471 (R = −(CH2)7−NHSO2NH2, pCH2C6H4−CH2NHSO2NH2).1023

Figure 5. Skeletal system shown on top occurs in a number of agrochemicals. AY


Chemical Reviews

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inhibition in clinical trials.1031 Sulfamides attached to the benzodioxin bicyclic system somewhat similar to 474 above have been patented for treatment of epilepsy and related disorders.1032 The methylpyrrolidinyl sulfamides 476 (n = 1, R = Bn, 2-benzothiazolyl) have been patented as antibacterial agents.1033

Scheme 34. Synthesis of N-Acylsulfamides Using CSI

The pyrimidine ring system is another that features prominently in agrochemicals. The skeletal system shown in Figure 5 occurs in a number of compounds.1055−1057 The imidazole sulfamide 486 is active as a fungicide, an insecticide, and an acaricide and inhibits root tumor formation by Plasmodiphora brassicae.1058 The benzimidazolesulfonic acid derivatives 487 act as microbiocides and stop Phytophthora

7.3.7. Other Uses. Compound 476 (n = 1, R = −C6H4SO2NH2-p) and some closely related compounds have been patented as hypoglycemic agents to lower blood sugar levels,1034 and the same group reported compounds such as 476 (n = 1, 2, 3, R = NH2, 1-piperidinyl, morpholino, 1-pyrrolidinyl, substituted amino) for similar usage.1035 A series of Nhydroxysulfamides BocNHSO2NHR (R = H, OtBu, OBn, − OHN+Et3) has been synthesized and their antifungal, antiviral, and antiproliferative activities assessed.1036

Scheme 35. Preparation of N-Acylsulfamides from CSI and αHydroxyesters Leading to N-Sulfamoyloxazolidinones

The N-sulfamido 3-(heterocyclothio) propionamides R− S(CH2)2C(NH2)NSO2NH2 (R = various heterocycles) have been patented as gastric secretory agents,1037 some benzene ring compounds containing a side chain −(CH2)n−NSO2N− entity have been patented as antiarrythmic agents,1038 and a series of four cyclic organics with a sulfamide side chain have been patented as antiparasitic artemisinin derivatives (sesquiterpene endoperoxides).1039 The sulfamide-containing compound 477 has been patented as an antitumor agent1040 and 478 as an anticancer agent.1041 Imidazoquinoline sulfamides such as 479 are immune response modifiers,1042 and the arylpiperazine sulfamide 480 has been patented for treating obesity and related conditions.1043 The pyrrolidine sulfamide antibiotic 481 has been reported in a Japanese patent1044 and in a paper from a Chinese group.1045 The chroman sulfamide derivative 482 was active as an antiestrogen.1046 Tetramethylenedisulfotetramine (TETS) 383 is highly toxic to humans and mammals and has been used as a rodenticide,906 and a series of TETS analogs with the adamantine structure maintained has been prepared to examine their recognition by brain GABA-gated chloride channel and a cyclodiene-sensitive monoclonal antibody.1047

infestation in tomatoes and potatoes and Plasmopara viticola on vines.1059 The iminium salts 96 show fungicidal activity.404 The compound N-[(dichlorofluoromethyl)thio]-N′,N′-dimethyl-Np-tolylsulfamide 488 known as tolylfluanid has been proposed as an acaricide,1060 and later the phenyl compound Cl2FCS−

N(Ph)SO2NMe2 was the subject of several patents and is often used as an antimicrobial agent in synergistic mixtures of compounds to control Klebsiella pneumoniae1061−1063 and Tyrophagus putrescential.1064 Compound 489 has been used as a fungicide and microbiocide and was patented some years ago.1065 Hydrolysis of 488 to N′,N′-dimethyl-N-p-tolylsulfamide has been reported.1066 7.4.2. Applied. Poly[bis(3-silsesquioxanylpropylamino)sulfoxide and -sulfone have been prepared by polycondensation

7.4. Agrochemical and Applied Uses

7.4.1. Agrochemical. The triazole skeleton is prominent in a variety of fungicidal sulfamide compounds, and thus, compounds like 483 are useful for controlling fungal attack in plants.1048−1052 Related compounds such as 484 with an attached pyrazole ring are also effective as fungicides.1053 Compound 485 is a herbicide, and a number of derivatives have been synthesized.1054 AZ


Chemical Reviews

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The N-acylsulfamide introduced earlier in Figure 5, where R1 = Me and R = −NH, has been introduced as a broad spectrum herbicide known as AC 322,140.1076 An acylsulfamide 493 containing separate thiazole, furan, and benzene rings has been patented as a lysophosphatidic acid (LPA) receptor antagonist.1077

of triethoxysilylpropylamine with SOCl2 and SO2Cl2. Polymerization involves formation of the unstable intermediates [(EtO)3SiMe3NH]2SOn, n = 1 or 2. The polymers gave complexes with lanthanides, which allowed them to be isolated from mixtures of other metals.1067 Preparation of some other sulfamide polymers has been noted earlier in this review (see section 6.3 above).901−903 Novel asymmetrically substituted sulfamides R1NHSO2NHR2 (R1 = R2 = nC14H29, nC8H17 and R1 = nC14H29 and R2 = (CH2)3OCH2CH(OH)CH2OH) form hydrogen-bond-directed amphiphilic 2-D sheet assemblies, and they show high ability to induce gelation in various solvents.1068 This work has been extended with the synthesis of those sulfamides with R1 = nC8H17 and R2 the same as above and the discovery that the compound with R1 = nC14H29 and R2 = −(CH2)6O(CH2CH2O)Me forms micrometer-sized giant vesicles in water.1069 A thermochemical study of the complexation of sodium Nchloro N′-benzenesulfamide PhNHSO2NHCl with transition metals at 298.1 K has been published.1070

Acyl chlorides RCOCl (R = alkyl, cycloalkyl, aryl, heterocycle) in sulfolane or toluene with sulfamide and heating at 120−180 °C affords nitriles with excellent yields. In the reaction the initial product is the acylsulfamide R(CO)NHSO2NH2, and it can be isolated under certain conditions.1078 7.5.2. Reactions. The strategy outlined above for preparation of N-acylsulfamides using CSI, alcohols, and amines1071,1072 has been adapted for use in construction of naturally occurring amino acid esters and nucleosides.1079

7.5. N-Acylsulfamides

7.5.1. Synthesis. More than 20 N-acylsulfamides have been synthesized in generally excellent yields using chlorosulfonylisocyanate (CSI) and alcohols followed by dry amines as shown in Scheme 34 (R was iPr, nBu, 1-adamantyl, phenyl, and pMeOC6H4, R1 = H, Me, Et, Bn, 1-adamantyl, and phenyl, and R2 = H, Et, and Bn).

A new symmetric sulfamide incorporating two oxazolidinone molecules, prepared from CSI or SO2Cl2 and oxazolidinone and 2-haloethanol, can be used to carbamoylate amines, and both mono- and dicarbamoylated products can be formed under controlled conditions.1080

Burgess-type intermediates, carboxysulfamoylammonium salts, form during the reaction from water. Sensitive N(chlorosulfonyl)carbamates formed initially, and these react with the added amines to give the acylsulfamide products.1071 Chlorosulfonylisocyanate (CSI) and α-hydroxyesters react to give after treatment with amines the N-acylsulfamides 490 (Scheme 35) in ∼80% yields, and these can be reacted under Mitsunobu conditions to give the N-sulfamoyloxazolidinones 491 in ∼65% yield.1072 A new Burgess-type sulfamoylating agent 492, prepared from CSI and tBuOH in CH2Cl2 followed by reaction with DMAP, reacts with primary and secondary amines to give N-acylsulfamides, RNHSO2N(CO)OBut, in yields of 78−100% (R aliphatic) and 35−50% (R aromatic).1073 A solid-phase synthesis of compounds containing the Nacylsulfamide motif has been carried out using CSI again and a Wang resin linked −OH group by reaction with amines giving polymer-bound sulfamoylcarbamates which on heating in THF

The acylsulfamides ArCH2OCONHSO2NHAr,1 easily obtained from CSI in a one-pot reaction, on thermal decomposition are a source of highly reactive benzyl cations.1081 Ring-opening metathesis oligomers incorporating sulfamides for organic synthesis have been reported and used to prepare, for example, the sulfamide 494 by a ring-closing metathesis and carbamate cleavage.1082 Almost 30 reactions leading to acylsulfamides by a new route have been realized involving a palladium-catalyzed reaction with Pd(dppf) 495 in dioxane of sulfamides R1R2NSO2NHR3 and aryl and heteroaryl halides giving R1R2NSO2NR3COAr in 36−92% yields.1083 The same researchers advanced this work using again Pd catalysts of various types and microwave radiation to react aryl and heteroaryl halides with sulfamide nucleophiles and Mo(CO)6 as a source of CO giving similar acyl sulfamides. The yields vary from 46% to 94%.1084

followed by reaction with a second amine gave R1NHSO2NH(CO)NHR2 in good yields.1074 Synthesis of 3-chloropropoxycarboxylsulfamide, NH2SO2NH(CO)O(CH2)3Cl, and its cyclization to perhydro-1,3-oxazin2-one sulfamide has been reported.1075 BA


Chemical Reviews

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trithiatraazine-1,1,3,3,5,5-hexoxide 505 was analyzed and its structure established.1094 Some very large structures have also had their structures determined. The heterocyclic system with a 10-membered ring

Scheme 36. Tautomers of 1,2,6-Thiadiazine 1,1-Dioxides

including the sulfamide moiety 506 has been prepared and had a structural determination carried out.1095 The authors made several of these types of compounds. Structural determinations of a number of 2-thia-1,3,5-triaza-7-phosphaadamantane 2,2dioxides including 507 and 508 have been done.1096 Condensation of N,N′-dialkylsulfamides with glyoxal leads to the new heterocyclic system bis-6,8-dialkyl-2,4-dioxo-7-thia-6,8diazabicyclo[3.3.0]octane 7,7-dioxides 509 and other com-

8. CYCLIC SULFAMIDES 8.1. X-ray and Computational Studies

The X-ray crystal structure of the platinthiadiazetidine 1,1dioxide 496 has been reported together with details of its preparation and reactivity. Some details are also given of the related phosphorus analog platinadiazaphosphetidine 2-oxide where phosphorus replaces sulfur and one of the oxygens of 496 is replaced by phenyl.1085 Much work has been done on the structures of 5-membered rings incorporating the sulfamide motif. Thus, the synthesis and properties of compounds 497 (X = O, NH) have been described, and X-ray structures of the 3-oxo (497, X = O, R = 1-naphthyl) Scheme 37. Tautomers of 4-Amino-1H-pyrazino[2,3-c] [1,2,6]-Thiadiazine 2,2-Dioxides

pounds (where R1 = R2 = Me, Et, nPr, iPr, nBu and R1 = Me, R2 = Et). X-ray diffraction analysis was performed on 509.1097 The unusual tantalum(V) cyclic sulfamide complex 510 has been the subject of an X-ray crystallographic study.1098 Ab initio theoretical calculations using different basic sets were carried out by a Spanish group on the three tautomers of 1,2,6thiadiazine 1,1-dioxides (Scheme 36), and it was found that the relative stability of the tautomers was in the order NH > CH > OH.1099 Using ab initio methods at the Hartree−Fock and MP2 levels, local density functional ab initio methods, and the semiempirical ab initio method SAM1 and X-ray structural data from CSD the same Spanish group looked at a number of sulfamide-containing heterocycles including some with fused heterocyclic rings. Comparing the experimental results (dipole moments, carbon13 NMR shifts) with the theoretical results none of the methods studied was adequate to describe the geometry and electronic properties of the molecules.1100 Finally, they performed a study of the tautomerism of 4-amino-1H-pyrazino[2,3-c][1,2,6]thiadiazine 2,2-dioxide (Scheme 37) in the gas phase carried out using semiempirical, MO, and DFT methods. Good

and 3-imino 497 (X = NH, R = Ph) have been determined.1086 The X-ray structure of 4,4-diphenyl-1,2,5-thiadiazolidine-3-one 1,1-dioxide 498 has been determined as part of a wider study of 1,2,5-thiadiazolidine-3-one 1,1-dioxide chemistry which is of interest because of their potential anticonvulsant activity.1087 Structures of compounds 499 and the alicyclic sulfamide

Me(NO2)NSO2N(NO2)Et have been published by a Zelinsky Institute group.1088 Structures of several more complex systems with a 5membered sulfamide entity incorporated have been published. The structure of the 1,2,5-thiadiazole 1,1-dioxide 500 has been determined very recently,1089 and the X-ray crystal structure of compound 501 has been reported.1090 A general synthesis of n-membered (n = 0−10) cyclic sulfamides has been developed, and the X-ray crystal structure of 502 (n = 1) has been determined.1091 The X-ray crystal structure of 503 has also been determined.1092 There are two reports on the structure of “trisulfimide” derivatives. In the first the trisilylated structure 504 was determined,1093 and in the second triammonium 1,3,5,2,4,6-

agreement was found between the UV spectroscopy results and the calculations.1101 A combined theoretical and spectroscopic study of 4,6-di-Oacetyl-2,3-dideoxy-D-erythro-hex-2-enopyranosyl sulfamide 511, which shows selectivity for inhibiting isoform IX of CA, has been BB


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carried out. The α anomer is more stable than the β anomer, and the calculated α/β ratio is about 95:5, which is in excellent agreement with the experimental data.888 Several cyclophanes incorporating a cyclosulfamide motif have been reported, and X-ray crystal structures of three and of cyclosulfamide, i.e., 499 (with H replacing NO2), have been reported.1102

giving regioselective 518 in yields averaging about 70%.1108 Cycloaddition of sulfamide and NCCN gave 75% 3,4-diamino1,2,5-thiadiazole dioxide 519 (R1 = R2 = NH2). Transamination

8.2. Synthesis

8.2.1. Reviews. A 2000 review by Gazieva with 112 references titled “sulfamides in the synthesis of heterocyclic compounds” is useful,1103 and a 2003 review on the synthesis and reactivity of cyclic sulfamidites (sulfamates) and sulfamidate (sulfamides) by Lubell566 with 66 references covers the field well up to that time.

of this compound with excess amine RNH2 gave 70−80% thiadiazoles 519 (R1 = R2 = NHR).1109 Diamination of conjugated dienes MeCHCHCHCH2 using Cu(I) as catalyst and N,N-di-tert-butylthiadiaziridine 1,1dioxide gave sulfamides 520 in ∼70% yields.1110 Many years ago Knollmuller synthesized the thiatriazole sulfamides 521 (R3 =

A 2004 review by Nicolaou on “new uses for the Burgess reagent in chemical synthesis” lists all important characteristic data for 187 compounds dealt with in the review (∼100 references).1104 8.2.2. Four-, Five-, Six-, and n-Membered Rings. The platino phosphorus-containing sulfamide ring compounds 512 and 513 have been synthesized in yields of ∼55% and 40%, respectively.1105 Numerous five-membered rings incorporating the sulfamide moiety have been synthesized. Rhodium-catalyzed transfer hydrogenation of 2,3-dihydro-[1,2,5]-thiadiazole-1,1-dioxide derivatives gave 514 in excellent yields with % ee ≥ 97.572 Starting from N-benzoylamino acids and chlorosulfonylisocyanate cyclic sulfamides 515 (X = Boc) form, and these can undergo Boc deprotection by fusion under reduced pressure to give 515 (X = H) in 90%+ yields.1106 Compounds 516 (R = Bn, nBu, Ph, and p-X-C6H4 (X = NO2, Br, −CN, etc.) have been synthesized in ∼50% yield from reaction of sulfuryl chloride with 2-chloroethylamine hydro-

Et2N) with various R1, R2, and R3 groups starting from Et2NCl NSO2Cl and R1NHNHR2.1111 His group also prepared the tetrazine 522 and the triazole 523.1112 Symmetrical β-amino α,β-unsaturated ketones RCOCH CRNH2 (R = Me, Ph, tBu) cyclize with sulfamide to give thiadiazines 524 (R1 = R2 = Me, Ph, tBu, R3 = H), while unsymmetrical β-amino and β-chloro β-unsaturated ketones cyclize with N-benzylsulfamide to give similar compounds.1113 Synthesis in high yields of nonsymmetrical sulfamides using Burgess-type reagents Et3N+SO2N−CO2Y (Y = CH2CHCH2 Me, Bn) is the subject of a patent and contemporaneously a paper by the Nicolaou group. An efficient, one-step synthesis of

many classes of N,N′-differentiated sulfamides using a wide range of aminoalcohols R1NHCR2R3−(CH2)n−C(OH)R4R5 and amines is described. Compound 525 is a typical product made in 62% yield from β-aminoethanol and the Burgess reagent with Y = Me in the general formula above.1114,1115 The six-membered sulfamide rings 526 (R = H, Bn) were prepared by cyclocondensation of N-arylidenesulfamides RNHSO2NCHAr with (EtO)2CHCH2CO2Et in TFA.1116 Compounds 527 (R = Me, Et, nPr, iPr, nBu, iBu, tBu, and npentyl) have been synthesized from sulfamide and 2-(2,4-

chloride followed by treatment with a primary amine and triethylamine and then ring closure with potassium carbonate in DMSO. The method can be adopted to allow preparation of 1,2,6-thiadaizinanes.1107 1,2,5-Thiadiazolidines can also be prepared by reaction of the sulfamoyl aziridine 517 with primary amines in DMSO at 100 °C BC


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Ring-closing metathesis has been used to synthesize other constrained sulfamides such as 534, and two strategies have been used in this approach. In the first, allylated sulfamides have been

dioxopentan-3-yl)benzoic acid, Me(CO)CH(CO)(oCO2HC6H4), in various alcohols.1117 Cyclic imido ethers react with sulfamide to give the sulfamoylamidines 528 (n = 1, 2 3, 4) in 70−80% yields, and these compounds undergo condensations with aliphatic and aromatic aldehydes to give thiatriazine dioxides 529 in 50−95% yields.1118 Various tautomers of 529 arise, and the ratios depend on temperature, solvent polarity, and substituents. employed, and in the second, butoxy acylsulfamides are used.1122 In a follow-up paper the same researchers outline strategies for synthesizing symmetric and unsymmetric cyclic sulfamides such as 535.1123 Later they synthesized 9−11-membered rings incorporating an extra nitrogen or oxygen into the cyclic sulfamide ring system giving compounds such as 536. To achieve this they used 3-component coupling, Mitsunobu alkylation, and ring-closing metathesis and the secondgeneration Grubbs catalyst.1124

The unusual phosphorus−nitrogen−sulfur six-membered ring c o m p o u n d 5 3 0 h a s b e en sy n t h e s iz e d f r o m b i s(diphenylphosphino)methane, Ph2P(CH2)3PPh2, sulfamide, and diethyl azodicarboxylate (DAD), EtO 2 CNN CO2Et, but the major product was the open-chain compound NH2SO2NPPh2CH2P(O)Ph2.1119 Quite a few seven-

The synthesis and X-ray crystal structure of the dithiatetrazocine 537 and the permethylated derivative 537 (R = Me) have also been reported.1125 A general method for synthesis of n-membered cyclic sulfamides has been reported. Starting from 538 a −(CH2)nBr

membered ring compounds incorporating the sulfamide moiety have been made. The sulfamides 531 (R = Boc, H, Bn, Me and Et) were made in 77−90% yields by ring-closing metathesis of CH2CFCH2NR1SO2NBnCH2CHCH2 in the presence of a ruthenium alkylidene carbine complex in dichloromethane at 40−100 °C.1120 In further similar studies the same group prepared 532 (R = Boc, Me, and Bn) and 533.1121

group is introduced on the nitrogen with the carboxy group, and this cyclizes in DMSO with NaOH to give 502 (n = 2−12).1091 8.2.3. Multiring Heterocycles. A number of bicyclic rings with the sulfamide moiety involved with both such as 5391126 or more commonly with one ring 5401127 have been reported. BD


Chemical Reviews

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Compounds 539 (R = H, K) were prepared from 8-nitroquinoline in two steps. Compounds 540 (R1 = MeO(CH2)2−, m,p(OCH2O)C6H3CH2−, etc., R2 = Ph, p-MeOC6H4−, etc.) were prepared from 2,3-diaminopyrazines under microwave conditions to give yields of 74−90%.

α-Sulfamidoalkylation has again been used to make the multicyclic sulfamide 556 (R1 = MeO, R2 = H; R1 = R2 = MeO)

starting from substituted N,N′-dibenzylsulfamides with formaldehyde in formic acid.1141 8.2.5. Sulfahydantoins: Five- and Six-Membered Rings. Cyclization of carboxy sulfamide derivatives of amino acids gives rise to the sulfahydantoins 557 in 71−84% yields without racemization.1142 Later this report was elaborated on, a series of

A general route to substituted sulfamides starting from 1,2dianilines with one nitrogen having the p-methoxybenzyl protecting group (PMB) attached is available. Sulfamide products such as 541 and 542 have been synthesized using this approach.1128

chiral sulfahydantoins was synthesized by alkaline intramolecular cyclocondensation, and compounds such as the pseudo nucleoside 558 were made.1143 Reaction of 557 (R = Me, Bn) with hydroxyacids gave unexpectedly O-substituted compounds 559 rather than Nalkylation products.1144 Sulfahydantoins, such as 557, have been exploited as peptide constraints, and this induces a unique backbone conformation with coplanarity of two consecutive peptide bonds.1145 A synthetic strategy employing reactions on an oxime resin has allowed the solid-state, efficient preparation of a large number of

Bromoallenes such as BnNHSO2NHCH2C(CH2OR)2CH CCHBr undergo regioselective cyclocondensation reactions to yield bicyclic sulfamides 543 in 90% yield.1129 Treatment of Nsulfonyl ketimines with various carbon nucleophiles in the presence of BF3·OEt2 gives 544 in yields of 35−84%.1130 Compounds 545 (R = Br, o-CNC6H4) have been reported recently in a patent.1131 A synthesis described above for cyclic

sulfamates can also be used to synthesize bicyclic sulfamides in ≥96% yield with % ee ≥96.569 8.2.4. Macrocyclic Heterocycles. Various novel heterocyclic sulfamide compounds such as 546 have been reported.1132 The same group carried out an α-ureidoalkylation of sulfamides giving compounds such as 547.1133 The complex sulfamides 548 and 549 have been synthesized by Rebek’s group.1134,1135 A series of cyclophanes, such as 550 (n = 1, 3, 5), containing the sulfamide moiety, has also been reported.1102 They also developed a general, a mild, and an efficient route for synthesis of sulfamides of type 551 (Y = Bu4N+, Cs+).1136 Syntheses of sulfamides 78 and 552 have been reported by the Dusemund group.359,1137 The dithiatetraazadiborocine 553 has been made by reaction of (NMe 2 SiMe 3 ) 2 SO 2 with (Me2N)2BCl.1138 α-Sulfamidoalkylation has been used to synthesize cyclic sulfamides such as the dithiatetrazocinedicarboxylate tetroxide 554 made in 74% yield from BnNHSO2NH2 and EtO2CCH(OEt)2 in the presence of TFA.1139 The spiro sulfamide phosphoranes 555 (R = MeO, CN, Me2N, N3) have been synthesized by reaction of 555 (R = Cl) with azide ion and trimethylsilyl compounds.1140

sulfahydantoin derivatives, such as 560 (R = H, CH2CHCH2), without racemization.1146 A range of sulfahydantoins have been synthesized from αamino esters, R1NHCHR2CO2R3, and sulfamide, and DBU at 160 °C neat, and a 6-membered analog 561 has been prepared was synthesized many years ago.1148 The herbicide Bentazon 87 is a bicyclic 6-membered sulfamid, and its preparation has been described in a patent.1149 8.3. Reactions

8.3.1. Metal-Catalyzed and Chiral Auxiliaries. Cyclic sulfamides such as 564 have been obtained in 34−83% yield by intramolecular diamination of benzyl-substituted sulfamides, e.g., 563 → 564, using a copper(II) acetate catalyst.1150 This work has been extended to achieve the synthesis of other cyclic sulfamides in excellent yields using copper(II) carboxylates, such as neodecanoate, and chiral copper(II) triflate· bis(oxazoline) complexes.949 BE


Chemical Reviews

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The cyclic sulfamide (S)-2-benzyl-4-isopropyl-1,2,5-thiadiazolidine 1,1-dioxide, 569, reacted with RCHO (R = iPr, Ph, nPr, and cyc-hexyl) to give ∼90% yields of 570 with dr of >99:1. Products 570 are readily hydrolyzed with LiOH at 0 °C in aqueous TFA to give back the corresponding carboxylic acid and the auxiliary.1155 8.3.2. Five-Membered Rings (Thiadiazole 1,1-Dioxides). Acid-catalyzed cycloaddition of N-substituted sulfamides Introduction of CC into various carbocycles and heterocycles can be neatly executed using N,N-di-tert-butylthiadiaziridine 1,1-dioxide 565 giving yields of 48−95%.1151 A review (>45 references) on “palladium- and nickel-catalyzed oxidative diamination of alkenes: cyclic urea, sulfamide and guanidine building blocks” appeared in 2008.1152 The palladiumcatalyzed aerobic oxidative cyclization of allylic sulfamides leads to excellent yields of the corresponding cyclic sulfamides with dr ranging from 6:1 to 30:1. Two possible mechanisms are envisaged for the reaction: aminopalladation of the alkene followed by β-hydride elimination or allylic C−H activation to give a π-allylpalladium intermediate and then C−N coupling.1153 A review of “recent progress in transition metal catalyzed hydrofunctionalization of less activated olefins” has appeared recently, and the study includes consideration of the cyclization

RNHSO2NH2 and cyanogen NCCN gives yields of 62−76% of diamino-substituted 5-membered cyclic sulfamides 571, and these can easily be hydrolyzed to the corresponding oxo derivatives 572.1156 The unusual betaine complex 573 between triphenylphosphine and 3,3-dimethyl-1,2,5-thiadiazolidine 1,1-dioxide has been used for efficient coupling between alcohols and carboxylic or nitrogen acids in Mitsunobu-type reactions.1157 UV spectra of 3,4-diphenyl-1,2,5-thiadiazole 1,1-dioxide 574 indicates that strong interactions with protic solvents occur with formation of carbinolamine derivatives with MeOH and EtOH,

Scheme 38. Ring Contraction in the HNO2 Nitrosation of 1,2,6-Thiadiazine 1,1-Dioxides

and some new thiadiazoline derivatives with substituents at positions 4 and 5 have been prepared.1158 This Argentinian group explored the chemistry of these 1,2,5-thiadiazole-1,1dioxides extensively in a series of publications. The kinetics of hydrolysis of 572 (R = Ph(CH2)2, cyc-hexyl, and Bn) has been studied from 24 to 73 °C in buffered aqueous solutions to give the alicyclic compounds RNHSO2N C(NH2)CO2H, and these can hydrolyze further cleaving the CN bond to give sulfamide and oxalic acid derivatives.1159 A type of imine α-anion has been produced from 3-methyl-4phenyl-1,2,5-thiadiazole 1,1-dioxides, and it dimerizes and may also tautomerize to give 575 (X = CH2).1160 Addition of

of open-chain sulfamides to cyclic sulfamides (diamination reaction).950 Cyclic sulfamides have a role as chiral auxiliaries. Thus, the titanium enolate of 566 reacting with RCHO (R = Ph,

Me, iPr, and trans-MeCHCH−) gave 567 in yields of ∼90% with stereoselection of, at least, >95:5. The sulfamide auxiliary and the hydroxycarboxylic acids 568 can be released from the dialdol 567 in a sequence of steps.1154

amines YNH2 and amides in ACN and DMF to 574 to give 575 (X = NYH) has been looked at.1161 Reactions of 574 (including substituted phenyl) with diamides (urea, thiourea, N,N′-dimethylurea, dithioxamide, sulfamide, BF


Chemical Reviews

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etc.) provide a new route to tetrahydroimidazole 1,2,5-thiadiazol5-one 2,2-dioxide 576 by reaction of 574 with urea. A series of eight different compounds of this type have been prepared in ∼90% yields.1162 Further work in this area involving reaction with other nitrogen nucleophiles such as ethylenediamine and o-

8.3.4. Seven-Membered Rings, Bicycles, and Multiring Heterocycles. Reaction of the 7-membered cyclic sulfamides 589 (R1 = MeO, R2 = H, MeO) with 10% NaOCl and aqueous NaOH gave the corresponding phthalazines in ∼90% yield.1173 A series of cyclic sulfamides of type 590 has been prepared, and crystal structures of a few typical representatives were determined.1174 A few papers have appeared on bicyclic systems. Fused 1,2,6thiadiazine S,S-dioxides 591 (R = H, Me, n = 3; R = Me, n = 4) have been synthesized from 2-acetylcyclopentanones and -cyclohexanones and sulfamides in methanolic HCl. The tautomerism of these systems has been studied by experimental (carbon-13 NMR and CP/MAS spectra) and theoretical (semiempirical AM1 and PM3 calculations) techniques.1175 Some reactions have been performed on the pyrazino 1,2,6thiadiazine 2,2-dioxide bicyclic heterosystem 592 (R = Me, Et), giving direct nucleophilic substitution of Cl by NH2 with ammonia and methylation of the 4-amino group with MeNH2. The chemistry of 592 has been compared with that of the closely related fused pteridine system.1176 Synthesis of bicyclic sulfamides with 5-membered and larger rings, such as 593, has been achieved by tandem cyclization of bromoallenes, e.g., BnNHSO2NH(CH2)2CHCCHBr with a palladium catalyst.1177 Several tricycles incorporating the sulfamido moiety in one ring have been synthesized including 594, which are lumichrome isosteres.1178 It has been possible to prepare the labile sulfamide compound 595 by inserting SO2 into a precursor. Thermolysis of 595 leads to loss of SO2.1179

phenylenediamine has been reported.1163 Reactions of amines with phenanthro[9,10-c]1,2,5-thiadiazole 1,1-dioxide 577 have also been reported.1164 Reaction of Ar1CHNSO2NH2 with Ar2CH(MeO)2 (Ar1, Ar2Ph, substituted phenyl, 2-naphthyl) gives Ar1CH NSO2NCHAr2, which cyclizes with zinc/TMSCl to give 578 (55−95%), which can be cleaved to yield unsymmetrical 1,2diaryl ethanediamines 579.1165 Compounds 497 (X = NH, O) have been synthesized from sulfamide, metal cyanide, and an aldehyde; for 497 (X = NH, R = n-hexyl, Ph(CH2)2−, Ph, 1- and 2-naphthyl, etc.) and for 497 (X = O, R = Ph, Ph(CH2)2, and 1-naphthyl). X-ray structures have been reported for representative members of each class.1086 8.3.3. Six-Membered Rings (Thiadiazine 1,1-Dioxides). An unusual ring contraction has been reported involving the dioxo 1,2,6-thiadiazine 1,1-dioxides 580. This subsequently, after nitrosation with HNO2, gave 581, which on mild acid treatment gave the 5-membered ring compound 582 (Scheme 38).1166 Reaction of sulfamide and N-substituted sulfamides with malonitrile was acid catalyzed to give 583, which hydrolyzes in mild acid to give 584.1167 The thiadiazine 1,1-dioxides 585 (R3 = H, 2-pyrimidinyl, 2pyridyl, 2-thiazolyl, etc.) are seen as possible hypoglycemic

8.4. Biological, Medicinal, Inhibition, and Other Uses

8.4.1. Reviews. The importance of sulfamides in biology and medicine is reflected in the titles of the reviews that have

agents, and they have been made by reaction of sulfonamides with HNO2 in the presence of R1OCCH2COR2 followed by cyclization with sulfamide in the presence of dry HCl.1168 1,2,6-Thiadiazine-1,1-dioxides can be converted into pyrazoles 586 (R = H) using NH2NH2, and N-methylsulfamide is also produced in good yield.1169 Compound 586 can also be accessed via flow vacuum pyrolysis at 550−700 °C of the same thiadiazine 1,1-dioxidesa reaction that has potential industrial significance for making pyrazoles.1170 Reaction of 587 with bulky amines RNH2 (R = iPr, tBu) afforded the pentadienoates 588 in ∼70% yield.1171 Bacterial cleavage using four different cultures has been reported for the nitrogen−sulfur bond in sulfamide, sulfamate, cyclamate, saccharin, and 1H-2,1,3-benzothiadiazin-4(3H)-one 2,2-dioxide.1172

appeared over the last 6 years that deal specifically with sulfamides alone. “The therapeutic potential of sulfamides as enzyme inhibitors” with more than 100 references was published BG


Chemical Reviews

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in 20061180 as was another review (>100 references) from the same group which concentrated on the theme “the sulfamide

symmetric and 7 symmetric) with different P2/P2′ substituents, and performed a comparative molecular field analysis (CoMFA) of these.1189

motif in the design of enzyme inhibitors” which also appeared in the same year.1181 A third review is titled “the role of sulfamide derivatives in medicinal chemistry: a patent review”, and it was published in The relationships between structure and interaction kinetics for HIV-1 protease inhibitors has been examined using 58 structurally diverse TS analog inhibitors which were analyzed by

a surface plasmon resonance biosensor. The P1/P1′ and P2/P2′ side chains were important and caused changes in association and dissociation rates.1190 Molecular modeling studies suggested that it would be possible to design HIV-1 protease inhibitors reaching between S1/S1′ and S2/S2′ binding sites by having ortho substitution of the P2/P2′ benzyl groups in the cyclic sulfamides that had been developed so far.1191 An article on the resistance profiles of cyclic and linear inhibitors of HIV-1 protease appeared about 10 years ago.1192 Using microwave heating a fast and selective palladium-catalyzed coupling reaction of cyclic sulfamide HIV-1 protease inhibitors has been reported. N-Amide arylation and aminocarbonylation reactions were carried out giving both nonsymmetric 601 (R1 = H) and symmetric 601 (R1 = R2) cyclic sulfamide products.1193 In recent work a library of 11 nonsymmetric cyclic sulfamide HIV-1 protease inhibitors has been synthesized using microwave heating and a silver(1) oxide catalyst leading to compounds 601 (R1 = H, Ph, Bn, PhCHCH, etc.; R2 = Ph, Bn, PhCH CH, Ph(CH2)2−).1194 Using a functionalized sulfamide scaffold a series of potential protease inhibitors 602 (R1 = CONH(CH2)2Ph, CO2Me, CONH(CH2)2-morpholino; R2 = Bn, m-PhOBn; R3 = H, Boc, CONH(CH2)2Ph, SO2Me, p-tolyl) has been prepared.1195 The same researchers used a surrogate cyclic sulfamide scaffold to identify compounds 603 (X = CH2, NH) as micromolar reversible inhibitors of human leukocyte elastase.1196 8.4.3. γ-Secretase and Other Enzyme Inhibitors. Several types of 5-membered cyclic sulfamides, such as 6041197 and 605,1198 have been patented as γ-secretase inhibitors, and the work has been reported on elsewhere also.1199 Sulfamide indolizidines 606 and 607 have been prepared to explore their potential as glycosidase inhibitors, and 606 was a totally selective inhibitor of α-mannosidase (Ki = 320 μM) and 607 twice as potent as an inhibitor of α-mannosidase (Ki = 150 μM).1200 A scaffold-hopping strategy using an array of heterocyclic scaffolds, in which the sulfamide group was replaced, to find new inhibitors of noroviruses has been employed. Compounds of types 608 with R shown in 609 were identified.1201

2009 and covers 18 patents that appeared during the time span given, i.e., 2006−2008.1182

8.4.2. CA and Protease Inhibitors. The boron-containing arylsulfamide 381 was very ineffective when tested as a CA inhibitor using isozymes I, II, and IX.1183 The sulfamide analogue of topiramate 10, compound 596, is 210 times less potent as an inhibitor of isozyme II of CA compared to the sulfamate-containing topiramate, but it does effectively inhibit isozymes CA, VA, VB, VII, XIII, and XIV. The weak binding with CA II is attributed to a clash between one inhibitor methyl group and Ala65.1184 Sulfamide derivatives such as 597 can act as metalloproteinase inhibitors.1185 The 8-membered cyclic sulfamide 598 was a poor inhibitor of HIV-1 protease compared to its 7-membered cyclic

urea analogue.1186 The same group has patented sulfamides of type 599 as HIV-I protease inhibitors.1187 The cyclic sulfamide HIV-1 protease inhibitor 600 when cocrystallized with HIV-1 protease adopted an unexpected conformation in which the P1′ and P2′ side chains were transposed.997 The same researchers extended this study to look at some other 7-membered cyclic sulfamides related to 600.996 In further work they added ketoxime groups to the P2/P2′ side chains,1188 prepared a set of 18 cyclic sulfamides (11 nonBH


Chemical Reviews

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principally in the field of nitrogen−sulfur(VI) chemistry, especially involving sulfamates and sulfamides.

Series of cyclic sulfamides of type 610 (R = H, Me, Et, CNMe, Bn, CH2CONH2, (CH2)2NC4H8O, etc.) have been evaluated as potential Norwalk virus inhibitors.999 8.4.4. Agonists and Other Uses. The thiadiazolidine-linked indole system 611 (R1 = R2 = R4 = R5, R3 = Me) has been patented as an agonist for the serotonin 5-HT1-like receptors.1202 Compounds 611 (R1 = R2 = Me, R3 = H, n = 1) and 611 (R1 = R2 = H, R3 = Me, n = 2) were also developed by the same group using a novel methiodide agent.1203 The 1,1-dioxo-1,2,6-thiadiazine-5-carboxamide derivatives 612 displayed both agonist and antagonist activity on cannabinoid receptors. Thus, 612 (R1 = Bn, R2 = p-ClC6H4, R3 = Ph) and 612 (R1 = Bn, R2 = p-ClC6H4, R3 = norbornyl) were agonists and 612 (R1 = Bn, p-ClC6H4, R3 = piperidinyl) acted as an antagonist for cannabinoid receptors.1204 Synthesis of some new pseudonucleosides containing chiral cyclic sulfamides such as 613 as aglycones has been described by an Algerian group.1205 These researchers also described the synthesis of various substituted 5-membered cyclic sulfamides using proteogenic amino acids and CSI in a Mitsunobu reaction.1206,1207 Building on compound 613 they synthesized other pseudonucleosides.1208 The alkynyl sulfamide 614 has been patented for treatment of Alzheimer’s disease.1209 A series of piperidine derivatives with a bicyclic sulfamide system attached such as 615 (R1 = H, p-Cl, etc.; R2 = H, Me) has been synthesized and pharmacological evaluation carried out.1210 The synthesis and antiproliferative activity of some novel sulfamides 616 (R = H, Me, Et, Bn, Boc) has been reported on recently.1211

Jean-Baptiste Malaubier obtained his Diploma in Chemistry from L’Institut Technologique de Poitiers, France, and following this, he completed his B.Sc. degree in Galway-Mayo Institute of Technology, Ireland. He then went on to complete his Ph.D. degree in Physical Organic Chemistry in the National University of Ireland, Galway under the supervision of Professor Spillane. Having completed his Ph.D. degree in 2010, he has been working in various roles in Roche Ireland Pharmaceuticals, providing technical support to the production of a range of active pharmaceutical ingredients (APIs). His interest remains in the chemistry of the nitrogen−sulfur entity.

ACKNOWLEDGMENTS AUTHOR INFORMATION

W.J.S. thanks the School of Chemistry, NUI Galway, for facilities during the writing of this review. Both authors would like to thank Dr. Mary Treasa Lohan, School of Chemistry, NUI Galway, for help with the diagrams.

Corresponding Author

*E-mail: [email protected]. Phone: +353 91492475. Notes

The authors declare no competing financial interest.

ABBREVIATIONS acac Bmin Boc CAI Cbz C3MIm Cp*RhCl (TsDPEN)

Biographies

CSI CuTC DABCO DASI dba DBU DEA DMA DMB DMAP DMTr ee EWG Fmoc bsCA hCA hpCA

Professor William J. Spillane holds B.Sc. and Ph.D. degrees from University College, Cork and received his D.Sc. degree from the National University of Ireland in 1992. He has lectured and researched at University College, Galway, now NUI, Galway, for many years and published more than 120 scientific papers and reviews. In 2008 he was elected a member of the Royal Irish Academy. He has spent extended periods on postdoctoral/sabbatical stays and worked in the University of Sussex (UK), University of Amsterdam (Netherlands), Université d’Aix Marseilles III (France), now AMU, UCSB (US), and University of Reading (UK). His research in mechanistic and taste studies has been BI

acetylacetonate 1-butyl-3-methylimidazole tert-butoxycarbonyl carbonic anhydrase inhibitor carboxybenzyl 1-propyl-3-methylimidazolium pentamethylcyclopentadienyl-Ts-1,2-diphenylethylenedamine chlorosulfonylisocyanate copper(I) thiophen-carboxylate 1,4-diazabicyclo-[2.2.2]octane dual aromatase−steroidal sulfatase inhibitor dibenzylideneacetone 1,8-diazobicyclo [5.4.0]-7-undec-7-ene diethylamine N,N-dimethylacetamide 4,4-dimethoxy-2-butanone 4-dimethylaminopyridine 4,4-dimethoxytriphenylmethyl chloride enantiomeric excess electron-withdrawing group fluorenylmethoxy carbonyl Brucella suis carbonic anhydrase human carbonic anhydrase Helicobacter pylori carbonic anhydrase


Chemical Reviews stCA LHDMS MEM MES MOM Ni(cod)2 NCS NSSI OTf OTHP PEG PCy3 9-Ph-9-FL PMB PTZ Rh2(esp)2 Ru2(hp)4Cl SSI TBAF TBDMS TFE TFA THB TMEDA TMSCl

Review

(20) Fukami, T.; Kyan, T.; Nakano, K.; Chen, R. H. Cryst. Res. Technol. 2011, 46, 287. (21) Schreuer, J. Z. Kristallogr. - New Cryst. Struct. 1999, 214, 306. (22) Meinhart, A.; Haussühl, E.; Bohatý, L.; Tillmanns, E. Z. Kristallogr. 2001, 216, 513. (23) Schreuer, J. Z. Kristallogr. - New Cryst. Struct. 1999, 214, 307. (24) Schreuer, J. Z. Kristallogr. - New Cryst. Struct. 1999, 214, 309. (25) Schwarz, S.; Thieme, I.; Richter, M.; Undeutsch, B.; Henkel, H.; Elger, W. Steroids 1996, 61, 710. (26) Simonov, Y. A.; Dvorkin, A. A.; Fonar, M. S.; Ganin, E. V.; Kotlyar, S. A. J. Inclusion Phenom. Mol. Recognit. Chem. 1991, 11, 1. (27) Mel’nyk, O. P.; Schollmeyer, D.; Olijnyk, V. V.; Filinchuk, Y. E. Acta Crystallogr., Sect. C: Cryst. Struct. Commun. 2001, C57, 151. (28) Filinchuk, Y. E.; Mel’nyk, O. P.; Mys’kiv, M. G. Pol. J. Chem. 2000, 74, 385. (29) Mel’nyk, O. P.; Filinchuk, Y. E.; Schollmeyer, D.; Mys’kiv, M. G. Z. Anorg. Allg. Chem. 2001, 627, 287. (30) Bekdemir, Y.; Kutuk, H.; Celik, S.; Yilmaz, V. T.; Thoene, C. J. Mol. Struct. 2002, 604, 239. (31) Yilmaz, V. T.; Andac, O.; Yazicilar, T. K.; Kutuk, H.; Bekdemir, Y.; Harrison, W. T. J. Mol. Struct. 2002, 608, 71. (32) Angerer, P.; Tillmanns, E.; Wildner, M. Croat. Chem. Acta 1999, 72, 295. (33) Liu, Z.-D.; You, Z.-L.; Zhu, H.-L.; Tan, M.-Y. Inorg. Chem. Commun. 2004, 7, 1292. (34) Athimoolam, S.; Natarajan, S. Acta Crystallogr., Sect. E: Struct. Rep. Online 2006, E62, o4219. (35) Rajkumar, B. J. M.; Ramakrishnan, V.; Bahadur, S. A. J. Raman Spectrosc. 1999, 30, 589. (36) Chertanova, L. F.; Gaer, S. A.; Sakovich, G. V.; Gareev, G. A.; Sopin, V. F. J. Struct. Chem. 1992, 33, 610. (37) Hope, H.; Nichols, B. G. Acta Crystallogr., Sect. B: Struct. Sci. 1981, B37, 158. (38) Leban, I.; Rudan-Tasic, D.; Lah, N.; Klofutar, C. Acta Crystallogr., Sect. B: Struct. Sci. 2007, B63, 418. (39) Paulus, E. F. Acta Crystallogr., Sect. B: Struct. Sci. 1975, B31, 1191. (40) Mehdi, S.; Rao, R. B. Acta Crystallogr., Sect. C: Cryst. Struct. Commun. 1984, C40, 1057. (41) Yavolovskii, A. A.; Ganin, E. V.; Fonar, M. S.; Simonov, Y. A.; Chumakov, Y. M.; Bochelli, G. Russ. J. Gen. Chem. 2004, 74, 1605. (42) Pecorari, P.; Rinaldi, M.; Costi, M. P.; Antolini, L. J. Heterocycl. Chem. 1992, 29, 1449. (43) Pecorari, P.; Rinaldi, M.; Antolini, L. Acta Crystallogr., Sect. C: Cryst. Struct. Commun. 1992, C48, 2027. (44) Shen, Y.-Z.; Xue, J.-J.; Li, Y.-Z.; Li, H.-L. Anal. Sci. 2005, 21, x89. (45) Ilczyszyn, M. M.; Wierzejewska, M.; Ciunik, Z. Phys. Chem. Chem. Phys. 2000, 2, 3503. (46) Denehy, E.; White, J. M.; Williams, S. J. Chem. Commun. 2006, 3, 314. (47) Costenzo, M. J.; Almond, H. R., Jr.; Gauthier, A. D.; Maryanoff, B. E. Tetrahedron: Asymmetry 1994, 5, 2459. (48) Haiges, R.; Wagner, R.; Boatz, J. A.; Yousufuddin, M.; Etzkorn, M.; Prakash, G. K. S.; Christe, K. O.; Chapman, R. D.; Welker, M. F.; Kreutzberger, C. B. Angew. Chem., Int. Ed. 2006, 45, 5179. (49) Lenin, M.; Balamurugan, N.; Ramasamy, P. Cryst. Res. Technol. 2007, 42, 39. (50) Belyaev, A. V.; Emel’yanov, V. A.; Khranenko, S. P.; Fedotov, M. A. Russ. J. Coord. Chem. 2001, 27, 184. (51) Langeslay, D. J.; Beni, S.; Larive, C. K. Anal. Chem. 2011, 83, 8006. (52) Mouli, V. C.; Sastry, G. S. Indian J. Pure Appl. Phys. 1989, 27, 101. (53) Akutsu, H.; Yamada, J.-i.; Nakatsuji, S. i. Chem. Lett. 2001, 3, 208. (54) Karaivanova, M. S.; Gjurova, K. M.; Petrova, R. P. Thermochim. Acta 1992, 198, 113. (55) Ilczyszyn, M. M.; Ilczyszyn, M. J. Raman Spectrosc. 2003, 34, 693. (56) Caldwell, G. W.; Sorgi, K. L.; Scott, L.; Maryanoff, B. E.; Maryanoff, C. A.; Masucci, J. A.; Nortey, S. O.; Sisco, W. R.; Micheel, A.; Ko, C.-Y. Org. Mass Spectrom. 1989, 24, 1051. (57) Xu, Y.; Yan, H.-K. J. Solution Chem. 1993, 22, 919.

Salmonella enterica serovar typhimurium carbonic anhydrase lithium hexamethyldisilazanide methoxyethoxymethyl maximal electroshock methoxymethyl nickel(cyclooctadiene)2 N-chlorosuccinimide nonsteroidal sulfatase inhibitor trifluoromethylsulfonate (triflate) tetrahydropyran-Opoly(ethylene glycol) phosphine tricyclohexylamine 9-(9-phenylfluorenyl)p-methoxybenzylamine pentylenetetrazole Rh2(α,α,α′,α′-tetramethyl-1,3-benzene dipropionate) tetrakis(2-oxypyridinato)diruthenium(II,III) chloride steroidal sulfatase inhibitor tetrabutylammonium fluoride tert-butyldimethylsilyl trifluoroethanol trifluoroacetic acid 1-trishomobarrelenyl N,N,N′,N′-tetramethylethylenediamine trimethylsilyl chloride

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Sulfamic Acid and Its N- and O-Substituted Derivatives - Chemical

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