Green and Efficient Synthesis of N-Sulfenyl Sulfoximines in Water

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Letter

Green and efficient synthesis of N-sulfenyl sulfoximines in water Yan Lin, Yanzhao Liu, Yang Zheng, Ruifang Nie, Li Guo, and Yong Wu ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.8b03549 • Publication Date (Web): 24 Sep 2018 Downloaded from http://pubs.acs.org on September 28, 2018

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ACS Sustainable Chemistry & Engineering

Green and efficient synthesis of N-sulfenyl sulfoximines in water Yan Lin+, Yanzhao Liu+, Yang Zheng, Ruifang Nie, Li Guo* and Yong Wu* Key Laboratory of Drug-Targeting and Drug Delivery System of the Education Ministry, Sichuan Engineering Laboratory for Plant-Sourced Drug and Sichuan Research Center for Drug Precision Industrial Technology, West China School of Pharmacy, Sichuan University, Chengdu, 610064, P. R. China Keywords: sulfoximines • sulfur • N-S coupling • water • green synthesis

Abstract: A new and metal-free cross-coupling reaction between sulfoximines and N(phenylthio)-succinimides was developed in water, afforded an efficient route for the synthesis of N-sulfenyl sulfoximines. This transformation provides N-sulfenyl sulfoximines with good functional group tolerance and moderate to excellent yields. Moreover, this protocol can be easily scaled up to the gram level with excellent yield.

Introduction With the rapid economic development worldwide, environmental concerns are of increasing interests. As a result, green chemistry that aims to reduce the toxic or polluting wastes in chemical processes has received much consideration in the past few decades.1,2 Generally, chemical pollution in the reaction system comes mainly from the use of organic solvents and

ACS Paragon Plus Environment

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metal catalysts. Therefore, the studies of environmental friendly solvents and catalysts have become one of the most fascinating areas in chemical research.3,4 In terms of the solvent, compared to the commonly used organic solvents, water is the most universal and friendly solvent in our ecosystem. It is a cheap, non-toxic, highly stable, non-flammable, easy handling and ‘green’ solvent.5 Some reports have demonstrated that water could accelerate the rate of reactions.6 Although many organic reactants suffer the poor aqueous solubility, water has still been widely used as solvent in chemical synthesis since Breslow’s pioneering work.7,8 On the other hand, to prepare green catalysts, the use of a recyclable heterogeneous catalyst in place of a single metal catalyst has been greatly developed and exhibits good catalytic activity in many reactions.9 However, defects still exist. For example, the synthesis of heterogeneous catalysts always needs multiple steps, and more efforts are required for structural identification. So, reactions proceeding in water with simple and eco-friendly catalyst are still highly desired. Organic compounds bearing nitrogen-sulfur bond are privileged structural motifs widely found in pharmaceutical and nature products.10,11,12 This fact induced extensive researchs on the construction of nitrogen-sulfur bond containing molecules over the years.13,14 Among them, as significant scaffolds, many attention were focused on the synthesis of sulfoximine derivatives due to their potential medicinal activity and high reactivity in organic synthesis. As pharmacophores, sulfoximines were associated with benzodiazepine receptor agonists,15 HIV-1 Protease Inhibitors,16,17 adrenergic receptor blockers18 and calcitriol analogues.19 In chemical synthesis, sulfoximines have been used as chiral ligands,20,21 organocatalysts22 and chiral directing groups in C-H activition.23,24 Fig.1 Approaches for the synthesis of N-sulfenyl sulfoximines


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In recent years, as the techniques of cross-coupling reactions are moving forward fastly, the formation of nitrogen-sulfur bond has been widely studied.13,14 However, the constructions of nitrogen-sulfur bond in water were rarely reported.25 As part of organosulfur-nitrogen containing compounds, many efforts were also made to form N-sulfenyl sulfoximines. Conventional methods to achieve N-sulfenyl sulfoximines often involve harsh conditions, where sodium hydride was needed (Fig.1, a).26 Recently, some alternative routes for the formation of Nsulfenyl sulfoximines have been established. For instance, N-trifluoromethylthiolated (Fig.1, b),27 copper-catalyzed N-thioetherification (Fig.1, c),28 iodine-catalyzed intermolecular S–N coupling reaction (Fig.1, d)29 were reported in the past three years. More recently, our team are also interested in the structural modification of sulfoximines. [Cu(DMAP)4I]I-catalyzed N-S bond formation method (Fig.1, e)30 and a recyclable heterogeneous copper nanomaterial catalyzed S–N formation route (Fig.1, f)31 were successfully eatablished for the synthesis of Nsulfenyl sulfoximines. Although these methods have proved efficiency in N-sulfenyl sulfoximines synthesis, more efforts have still been made in our group in terms of green and


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sustanability. Here, we report this green and efficient methodology for the metal-free Nthioetherification of sulfoximines in water. Results and discussion In our previous study, we found N-(phenylthio)-succinimide (2a) showed high reaction activity in the heterogeneous catalytic system, even if using water as the sole solvent (Table 1, entry 1).31 Moreover, in the absence of copper catalyst, 10% yield of N-sulfenyl sulfoximine (3aa) was also obtained (Table 1, entry 2). These results inspired us to continue to explore green and sustainable synthetic route for the construction of N-sulfenyl sulfoximines. With the above possibilities in mind, we are continuing to study this cross-coupling reaction using diphenyl sulfoximine (1aa) and N-(phenylthio)-succinimide (2a) as starting materials. Considering the solubility of the substrates in water, some solubilizing agents including glycerol, PEG400, PEG600, Triton X-770, sodium 1-dodecanesulfonate (SDS), sodium dodecylbenzenesulphonate (LAS),

sodium

lauryl

polyoxyethylene

ether

sulfate

(AES),

Tween

80,

benzyldodecyldimethylammonium bromide (DDBAB), benzyltriethylammonium chloride (TEBAC), tetrabutylammonium fluoride (TBAF) and tetrabutylammonium bromide (TBAB) were introduced (Table 1, entries 3-14). To our delight, with the adding of solubilizing assistant, the conversion rate and product yield were significantly increased. Among them, Tween 80 and TBAB shown higher activity (Table 1, entry 7 and entry 14). In addition, some reports revealed that cyclodextrin have substrate selective binding and catalytic activity in a wide scope of organic reactions,32,33 so cyclodextrin were also used in this reaction (Table 1, entries 15-17). Inspiringly, β-cyclodextrin shown excellent activity, the conversion rate and the yields were increased to 85% and 72% (Table 1, entry 16). When the temperature rised to 30 oC, the conversion rate was increased to 98% and the yield of 3aa was increased to 78% (Table 1, entry


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18). Further rising the temperature to 40 oC and 50 oC, no significant increase in yield (Table 1, entries 19-20). Meanwhile, continuing to rise the reaction temperature in the presence of Tween 80 or TBAB, the yield of 3aa was significantly improved, and the yield was increased to 90% at 50 oC with Tween 80 (Table 1, entries 21-26). These results showed that Tween 80 is more suitable for this coupling reaction. For the optimization of the amount of Tween 80, 2 equivalents were found to be suitable for this reaction (Table 1, entries 27-29). Finally, experiments to optimize the ratio of the reaction substrates were carried out and 2 equivalent weights 2a (base on 1aa) were appropriate (Table 1, entries 30-31). Table 1. Reaction optimization [a] O O Ph

NH S

Ph

1aa

+

N S 2a

O

additive H2O

O Ph

N

S Ph

S

Ph 3aa

Additive

Temp (oC)

Conversion 1aa (%)

Yield 3aa (%)

1

h-BN@Cu(II)

rt

80

75

2

--

rt

15

10

3

Glycerol

rt

trace

trace

4

PEG400

rt

47

40

5

PEG600

rt

44

39

6

Triton X-770

rt

53

45

7

Tween 80

rt

60

51

8

SDS

rt

7

trace

9

LAS

rt

27

18

10

AES

rt

66

49

Entry


5


Page 6 of 18

11

DDBAB

rt

49

40

12

TEBAC

rt

51

45

13

TBAF

rt

5

trace

14

TBAB

rt

60

53

15

α-cyclodextrin

rt

52

46

16

β-cyclodextrin

rt

85

72

17

γ-cyclodextrin

rt

trace

trace

18

β-cyclodextrin

30

98

78

19

β-cyclodextrin

40

100

78

20

β-cyclodextrin

50

100

79

21

Tween 80

30

72

60

22

TBAB

30

76

63

23

Tween 80

40

80

71

24

TBAB

40

100

80

25

Tween 80

50

100

90

26

TBAB

50

100

81

27

Tween 80

50

70

60b

28

Tween 80

50

80

72c

29

Tween 80

50

100

90d

30

Tween 80

50

78

70e

31

Tween 80

50

100

89f

a

Reaction condition: 1aa (50 mg, 0.23 mmol), 2a (0.46 mmol, 2 × 1.0 equiv./12 h),

additive (0.46 mmol, 2 equiv), H2O (4 mL), under air, 24 h. Isolated yields. b Tween 80 (1.0


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equiv). c Tween 80 (1.5 equiv.). d Tween 80 (3 equiv.). e 2a (0.35 mmol, 1.5 equiv.). f 2a (0.69 mmol, 3× 1.0 equiv./8 h). To evaluate the versatility and limitation of this method, we applied this procedure to the cross-coupling reaction of a wide range of sulfoximines with N-(phenylthio)-succinimide (2a) (Table 2). First, electron-donating groups substituted diphenyl sulfoximines were coupled with 2a and gave the corresponding N-sulfenyl sulfoximines in good yields (Table 2, 3aa-3ac). Next, diphenyl sulfoximines with electron-withdrawing groups, such as phenyl, acetyl, chlorine, trifluoromethyl, nitro, cyano were also successfuly reacted with N-(phenylthio)-succinimide, furnished the corresponding products in good to excellent yields (Table 2, 3ba-3bh). Compared with 3bh, when an electron-donating group methyl was added to sulfoximine, the yield was increased (Table 2, 3ca). In addition, S-phenyl-S-naphthalene-sulfoximine and S-phenyl-Spyridyl-sulfoximine were efficiently reacted with 2a, gave the products with yields 93% (Table 2, 3da) and 95% (Table 2, 3db), respectively. Furthermore, S-aryl-S-alkyl-sulfoximines and dialkyl sulfoximines were explored. S-phenyl-S-menhyl, S-phenyl-S-cyclohexyl, S-phenyl-S-benzyl– sulfoximines, generated the corresponding N-sulfenyl sulfoximines in excellent yields (Table 2, 3ea, 3ec, 3ed). Compared with 3ea (yield: 89%), may be limited by steric hindrance, S-phenyl-Sn-octyl-sulfoximine afforded the product in a lower yield (3eb, 47%). Dialkyl sulfoximines may be affected by both electronic effects and steric hindrance, afforded the desire products in low to excelent yields without obvious regularity (Table 2, 3fa-3fd). To investigate the efficiency and further practicality of this transformation, a gram-scale-up of the reaction using 1aa and 2a was performed. The corresponding product 3aa was obtained with 91% yield. Table 2 Substrate scope of sulfoximines with N-(phenylthio)-succinimide a


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a

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Reaction condition: 1 (0.23 mmol), 2a (0.46 mmol, 2 × 1.0 equiv./12 h), Tween 80 (0.46

mmol, 2 equiv.), in H2O (4 mL), 50 oC, under air, 24 h. Isolated yields; b 2a (0.69 mmol, 3 × 1.0 equiv./12 h), 48 h. Isolated yields; c Isolated yield on 5 mmol scale reaction.

Table 3 Substrate scope of diphenyl sulfoximine with N-thiosuccinimides a


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a

Reaction condition: 1aa (0.23 mmol), 2 (0.46 mmol, 2 × 1.0 equiv./12 h), Tween 80 (0.46

mmol, 2.0 equiv.), in H2O (4 mL), 50 oC, under air, 24 h. Isolated yields; b 2a (0.69 mmol, 3 × 1.0 equiv./12 h), 48 h. Isolated yields; Moreover, the scope of N-(phenylthio)-succinimides were also investigated. N-(phenylthio)succinimides with electron-donating groups and electron-withdrawing groups were reacting smoothly and furnished the corresponding products addition,

N-(alkylthio)-succinimides:

in high yields (Table 3, 3ga-3hd). In

N-(ethylthio)-succinimide

(2ia),

N-(t-butylthio)-

succinimide (2ib) and N-(n-octylthio)-succinimide (2ic) were tested in the standard conditions. To our disappointment, those N-(alkylthio)-succinimides

did not react with diphenyl

sulfoximine (Table 3, 3ic, 3ia, 3ib).


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Scheme 1. Control experiments

To gain further understanding about the reaction mechanism, control experiments were conducted. First, a radical capture experiment was performed and 2, 2, 6, 6-tetramethylpiperidine N-oxide (TEMPO) was used as additives in the reaction. With 2 and 4 equipments of TEMPO, the yield of 3aa was decreased from 90% to 50% and 30%, respectively (Scheme 1, a). This result implied that a radical pathway may be involed in this reaction. Next, performing the reaction under Ar and O2 atmosphere instead of air resulted in product 3aa with different yields, implying that oxygen cannot promote this cross-coupling reaction (Scheme 1, b). To further understanding the reaction pathway, the by-products were explored. When the reaction was conducted under O2, air and Ar for 24 h, the by-product 1,2-diphenyldisulfane (4) was isolated in different yields, 20%, 15%, 5% (based on 2a), respectively (Scheme 1, c). In this reaction, if 1,2diphenyldisulfane just come from the self-coupling of thiophenyl radical, the yields should be


10

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similar. So, the different yields of 4 implied that thiophenol may be existed and was further oxidized by oxygen to 4. This result indirectly proved that the radical of thiophenyl was subsistent and may further react with 1aa to generate thiophenol and diphenyl sulfoximine radical. In addition, 1,2-diphenyldisulfane cannot react with 1aa in the standard condition (Scheme 1, c). Scheme 2. Possible mechanism

Based on the aforementioned experimental results, a plausible mechanism for the crosscoupling reactions was proposed (Scheme 2). Initially, 2a was transformed into succinimide radical (5) and thiophenyl radical (6) under the standard condition. Then, the two radicals reacted with 1aa to form the diphenyl sulfoximine radical (7), by-products thiophenol (8) and dihydromaleimide (9). Finally, the diphenyl sulfoximine radical 7 undergoes group transfer with another 2a to form the desire product 3aa, and the succinimide radical 5 was regenerated. Conclusion


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In conclusion, a highly efficient protocol for the synthesis of N-sulfenyl sulfoximines have been developed through the metal-free cross-coupling reactions in water. This reaction proceeded well and has moderate to excellent yields with good functional group tolerance under air. The environmentally benign medium, metal-free condition and gram-scale capability make this reaction a green and practical approach for the synthesis of N-sulfenyl sulfoximines. Further study of the reaction mechanism and its applications are ongoing in our laboratory. Experimental section Procedure for the Synthesis of N-Sulfenyl sulfoximines (3aa-3aj): Sulfoximines (0.23 mmol, 1.0 equiv.) was added to a 25 mL round-bottom flask equipped with a magnetic stir bar. Then N-Thiosuccinimides (0.23 mmol, 1.0 equiv.), Tween 80 (0.46 mmol, 2.0 equiv.) and water (4 mL) was added. The reaction mixture was allowed to stir under air at 50 °C for 12 h. Then added N-thiosuccinimides (0.23 mmol, 1.0 equiv.) sequentially and allowed to stir for another 12 h. After completion of the reaction (monitored by TLC), the reaction mixture was cooled to room temperature and extracted with ethyl acetate (3 x 5 mL). The organic layer was combined, washed with brine, dried over anhydrous Na2SO4 and the solvent was evaporated to dryness. The crude residue was purified by flash column chromatography (EtOAc/Petroleoumether with 0.3% trimethylamine) to obtain the desired pure product. Corresponding Author *E-mail: [email protected] *E-mail: [email protected]. ORCID https://orcid.org/0000-0003-0719-4963 Present Addresses


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No.37.DaXue Road, Chengdu, Sichuan 610041, P.R. China Author Contributions [+] These authors contributed equally to this work. The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Funding Sources This work was supported by National Natural Science Foundation of China (Grant No: 81773577; 81573286; 81602954). Notes The authors declare no competing financial interest. REFERENCES (1) Anastas, P.; Eghbali, N. Green Chemistry: Principles and Practice. Chem. Soc. Rev. 2010, 39, 301-312, DOI 10.1039/b918763b. (2) Simon, M. O.; Li, C. J. Green chemistry oriented organic synthesis in water. Chem. Soc. Rev. 2012, 41, 1415-1427, DOI 10.1039/c1cs15222j. (3) Roscales, S.; Csákÿ, A. G. Transition-metal-free C-C bond forming reactions of aryl, alkenyl and alkynylboronic acids and their derivatives. Chem. Soc. Rev. 2014, 43, 8215-8225, DOI 10.1039/c4cs00195h. (4) Bhunia, A.; Yetra, S. R.; Biju, A. T. Recent advances in transition-metal-free carbon-carbon and carbon-heteroatom bond-forming reactions using arynes. Chem. Soc. Rev. 2012, 41, 31403152, DOI 10.1039/C2CS15310F.


13


Page 14 of 18

(5) Butler, R. N.; Coyne, A. G. Water: Nature's Reaction Enforcer-Comparative Effects for Organic Synthesis "In-Water" and "On-Water. Chem. Rev. 2010, 110, 6302-6337, DOI 10.1021/cr100162c. (6) Han, M. Y.; Lin, J.; Li, W.; Luan, W. Y.; Mai, P. L.; Zhang, Y. Catalyst-free nucleophilic addition reactions of silyl glyoxylates in water. Green Chem. 2018, 20, 1228–1232, DOI 10.1039/c7gc03775a. (7) Rideout, D. C.; Breslow, R. Hydrophobic acceleration of Diels-Alder reactions. J. Am. Chem. Soc. 1980, 102, 7816-7817, DOI 10.1021/ja00546a048. (8) Luque-Agudo, V.; Gil, M. V.; Román, E.; Serrano, J. A. "On water" reactivity between carbohydrate-derived nitroalkenes and furans. Green Chem. 2016, 18, 3844-3851, DOI 10.1039/c6gc00555a. (9) Corma, A.; García, H.; Xamena, F. X. L. Engineering Metal Organic Frameworks for Heterogeneous Catalysis. Chem. Rev. 2010, 110, 4606-4655, DOI 10.1021/cr9003924. (10) Miao, L.; Xu, L.; Narducy, K. W.; Trudell, M. L. First Multigram Preparation of SCP123, A Novel Water-Soluble Analgesic. Org. Process Res. Dev. 2009, 13, 820-822, DOI 10.1021/op900113b. (11) Brahemi, G.; Kona, F. R.; Fiasella, A.; Buac, D.; Soukupova, J.; Brancale, A.; Burger, A. M.; Westwell, A. D. Exploring the Structural Requirements for Inhibition of the Ubiquitin E3 Ligase Breast Cancer Associated Protein 2 (BCA2) as a Treatment for Breast Cancer. ́ J. Med. Chem. 2010, 53, 2757-2765, DOI 10.1021/jm901757t. (12) Dahl, R.; Bravo, Y.; Sharma, V.; Ichikawa, M.; Dhanya, R. P.; Hedrick, M.; Brown, B.; Rascon, J.; Vicchiarelli, M.; Mangravita-Novo, A.; Yang, L.; Stonich, D.; Su, Y.; Smith, L. H.; Sergienko, E.; Freeze, H. H.; Cosford, N. D. P. Potent, Selective, and Orally Available


14

Page 15 of 18 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Benzoisothiazolone Phosphomannose Isomerase Inhibitors as Probes for Congenital Disorder of Glycosylation Ia. J. Med. Chem. 2011, 54, 3661-3668, DOI 10.1021/jm101401a. (13) Chen, F. J.; Liao, G.; Li, X.; Wu, J.; Shi, B. F. Cu(II)-Mediated C-S/N-S Bond Formation via C-H Activation: Access to Benzoisothiazolones Using Elemental Sulfur. Org. Lett. 2014, 16, 5644-5647, DOI 10.1021/ol5027156. (14) Dou, Y. C.; Huang, X.; Wang, H.; Yang, L. T.; Li, H. Yuan, B.-X.; Yang, G. Y. Reusable cobalt-phthalocyanine in water: efficient catalytic aerobic oxidative coupling of thiols to construct S-N/S-S bonds. Green Chem. 2017, 19, 2491–2495, DOI 10.1039/c7gc00401j. (15) Satzinger, G. Drug discovery and commercial exploitation. Drug News Perspect. 2001, 14, 197-207, DOI 10.1358/dnp.2001.14.4.858403. (16) Lu, D.; Vince, R. Discovery of potent HIV-1 protease inhibitors incorporating sulfoximine functionality. Bioorg. Med. Chem. Lett. 2007, 17, 5614-5619, DOI 10.1016/j.bmcl.2007.07.095. (17) Lu, D.; Sham, Y. Y.; Vince, R. Design, asymmetric synthesis, and evaluation of pseudosymmetric sulfoximine inhibitors against HIV-1 protease. Bioorg. Med. Chem. 2010, 18, 2037-2048, DOI 10.1016/j.bmc.2010.01.020. (18) Ikeuchi, H.; Ahn, Y. M.; Otokawa, T.; Watanabe, B.; Hegazy, L.; Hiratake, J.; Richards, N. G. J. A sulfoximine-based inhibitor of human asparagine synthetase kills l-asparaginaseresistant leukemia cells. Bioorg. Med. Chem. 2012, 20, 5915-5927, DOI 10.1016/j.bmc.2012.07.047. (19) Kahraman, M.; Sinishtay, S.; Dolan, P. M.; Kensler, T.W.; Peleg, S.; Saha, U.; Chuang, S. S.; Bernstein, G.; Korczak, B.; Posner, G. H. Potent, Selective and Low-Calcemic Inhibitors of CYP24 Hydroxylase: 24-Sulfoximine Analogues of the Hormone 1α,25-Dihydroxyvitamin D3. J. Med. Chem. 2004, 47, 6854-6863, DOI 10.1021/jm040129.


15


Page 16 of 18

(20) Shen, X.; Zhang, W.; Ni, C.; Gu, Y.; Hu, J.; J. Am. Chem. Soc., 2012, 134, 16999-17002, DOI 10.1021/ja308419a. (21) Craig, D.; Grellepois, F.; White, A. J. P. Asymmetric decarboxylative Claisen rearrangement reactions of sulfoximine-substituted allylic tosylacetic esters. J. Org. Chem. 2005, 70, 6827-6832, DOI 10.1021/jo050747d. (22) Frings, M.; Thomé, I.; Bolm, C. Synthesis of chiral sulfoximine-based thioureas and their application in asymmetric organocatalysis. Beilstein J. Org. Chem. 2012, 8, 1443-1451, DOI 10.3762/bjoc.8.164. (23) Dong, W.; Parthasarathy, K.; Cheng, Y.; Pan, F.; Bolm, C. Hydroarylations of Heterobicyclic Alkenes through Rhodium-Catalyzed Directed C-H Functionalizations of S-Aryl Sulfoximines. Chem. Eur. J. 2014, 20, 15732-15736, DOI 10.1002/chem.201404859. (24) Huang, J. P.; Huang, Y. F.; Wang, T.; Huang, Q.; Wan, Z. H.; Chen, Z. Y. MicrowaveAssisted Cp*CoIII-Catalyzed C-H Activation/Double C-N Bond Formation Reactions to Thiadiazine 1-Oxides. Org. Lett. 2017, 19, 1128–1131, DOI 10.1021/acs.orglett.7b00120. (25) Wang, F.; Chen, C.; Deng, G.; Xi, C. J. Concise Approach to Benzisothiazol-3(2H)-one via Copper-Catalyzed Tandem Reaction of o-Bromobenzamide and Potassium Thiocyanate in Water. J. Org. Chem. 2012, 77, 4148−4151, DOI 10.1021/jo300250x. (26) Akutagawa, K.; Furukawa, N.; Oae, S. Preparation of S,S-diphenylsulfilimines, sulfoximines, and -N-(p-tolylsulfonyl)sulfonediimines N-substituted with sulfur groups of different oxidation states. Bull. Chem. Soc. Jpn. 1984, 57, 518-524, DOI 10.1246/bcsj.57.518. (27) Bohnen, C.; Bolm, C. N-Trifluoromethylthiolated Sulfoximines. Org. Lett. 2015, 17, 30113013, DOI 10.1021/acs.orglett.5b01384.


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(28) Zhu, H.; Yu, J. T.; Cheng, J. Copper-catalyzed N-thioetherification of sulfoximines using disulfides. Chem. Commun. 2016, 52, 11908-11911, DOI 10.1039/c6cc06359d. (29) Yang, L.; Feng, J.; Qiao, M.; Zeng, Q. Synthesis of N-sulfenyl-sulfoximines and sulfenamides through a metal-free N-H/S-H dehydrocoupling reaction. Org. Chem. Front. 2018, 5, 24-28, DOI 10.1039/c7qo00766c. (30) Peng, Y.; Lin, Y.; Nie, R.F.; Zheng, Y.; Liu, Y.Z.; Guo, L.; Wu, Y. A One-Pot Cascade Reaction by Combining NH-Sulfoximines with Thiophenols Under Mild Conditions. Eur. J. Org. Chem. 2018, 6, 844–850, DOI 10.1002/ejoc.201701643. (31) Lin, Y.; LÜ, G. H.; Liu, Y. Z.; Zheng, Y.; Nie, R. F.; Guo, L. Wu, Y. h-BN@Copper(II) nanomaterial catalyzed cross-coupling reactions between sulfoximines and N-(phenylthio)succinimide under mild condition. Catal. Commun. 2018, 112, 68–73, DOI 10.1016/j.catcom.203.8.04.021. (32) Crini, G. A History of Cyclodextrins. Chem. Rev. 2014, 114, 10940-10975, DOI 10.1021/cr500081p. (33) Floresta, G.; Talotta, C.; Gaeta, C.; De Rosa, M.; Chiacchio, U.; Neri. P.; Rescifina, A. gamma-cyclodextrin as a catalyst for the synthesis of 2-methyl-3,5-diarylisoxazolidines in water. J. Org. Chem. 2017, 82, 4631-4639, DOI 10.1021/acs.joc.7b00227.


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Tween 80 promoted cross-coupling reactions between sulfoximines and N-(phenylthio)succinimide in water: Efficient synthesis of N-sulfenyl sulfoximines


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Green and Efficient Synthesis of N-Sulfenyl Sulfoximines in Water

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