Recent Advances in Difluoromethylthiolation

Xuan Xiao; Zi-Tong Zheng; Ting Li; Jing-Lin Zheng; Ting Tao; Li-Mei Chen; Jin-Ying Gu; Xu Yao; Jin-Hong Lin; Ji-Chang Xiao

doi:10.1055/s-0039-1690714

Synthesis, Table of Contents

Synthesis 2020; 52(02): 197-207
DOI: 10.1055/s-0039-1690714

short review

Recent Advances in Difluoromethylthiolation

Authors

Xuan Xiao §

^aGroup of Lead Compound, Institute of Pharmacy & Pharmacology, Hunan Province Cooperative Innovation Center for Molecular Target New Drug Study, University of South China, Hengyang 421001, P. R. of China Email: yaoyao19840415@126.com

^bKey Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032, P. R. of China Email: jlin@sioc.ac.cn Email: jchxiao@sioc.ac.cn
Zi-Tong Zheng §

^aGroup of Lead Compound, Institute of Pharmacy & Pharmacology, Hunan Province Cooperative Innovation Center for Molecular Target New Drug Study, University of South China, Hengyang 421001, P. R. of China Email: yaoyao19840415@126.com
Ting Li

^aGroup of Lead Compound, Institute of Pharmacy & Pharmacology, Hunan Province Cooperative Innovation Center for Molecular Target New Drug Study, University of South China, Hengyang 421001, P. R. of China Email: yaoyao19840415@126.com
Jing-Lin Zheng

^aGroup of Lead Compound, Institute of Pharmacy & Pharmacology, Hunan Province Cooperative Innovation Center for Molecular Target New Drug Study, University of South China, Hengyang 421001, P. R. of China Email: yaoyao19840415@126.com
Ting Tao

^aGroup of Lead Compound, Institute of Pharmacy & Pharmacology, Hunan Province Cooperative Innovation Center for Molecular Target New Drug Study, University of South China, Hengyang 421001, P. R. of China Email: yaoyao19840415@126.com
Li-Mei Chen

^aGroup of Lead Compound, Institute of Pharmacy & Pharmacology, Hunan Province Cooperative Innovation Center for Molecular Target New Drug Study, University of South China, Hengyang 421001, P. R. of China Email: yaoyao19840415@126.com
Jin-Ying Gu

^aGroup of Lead Compound, Institute of Pharmacy & Pharmacology, Hunan Province Cooperative Innovation Center for Molecular Target New Drug Study, University of South China, Hengyang 421001, P. R. of China Email: yaoyao19840415@126.com
Xu Yao∗

^aGroup of Lead Compound, Institute of Pharmacy & Pharmacology, Hunan Province Cooperative Innovation Center for Molecular Target New Drug Study, University of South China, Hengyang 421001, P. R. of China Email: yaoyao19840415@126.com
Jin-Hong Lin∗

^bKey Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032, P. R. of China Email: jlin@sioc.ac.cn Email: jchxiao@sioc.ac.cn
Ji-Chang Xiao∗

^bKey Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032, P. R. of China Email: jlin@sioc.ac.cn Email: jchxiao@sioc.ac.cn

Abstract

All articles of this category

^§ These authors contributed equally to this work.

Abstract

The difluoromethylthio group (HCF₂S), which has been identified as a valuable functionality in drug and agrochemical discovery, has received increased attention recently. Two strategies, difluoromethylation and direct difluoromethylthiolation, have been well established for HCF₂S incorporation. The former strategy suffers from the need to prepare sulfur-containing substrates. In contrast, direct difluoromethylthiolation is straightforward and step-economic. This short review covers the recent advances in direct difluoromethylthiolation, including electrophilic, radical, and transition-metal-catalyzed or -promoted reactions.

1 Introduction

2 Electrophilic Difluoromethylthiolation

3 Radical Difluoromethylthiolation

4 Transition-Metal-Catalyzed or -Promoted Difluoromethylthiolation

5 Conclusions and Perspectives

Key words

difluoromethylthio group - difluoromethylthiolation - electrophilic - radical - fluorine

Full Text

References

References
1 Cahard D, Bizet V. Chem. Soc. Rev. 2014; 43: 135
2 Thayer AM. Chem. Eng. News 2006; 84 (23): 15
3 Organofluorine Chemistry . Uneyama K. Blackwell; Oxford: 2006
4 Kirsch P. Modern Fluoroorganic Chemistry: Synthesis, Reactivity, Applications, 2nd ed. Wiley-VCH; Weinheim: 2013

5a Fluorine in Medicinal Chemistry and Chemical Biology. Ojima I. Blackwell; Chichester: 2009
5b Wang J, Sánchez-Roselló M, Aceña JL, del Pozo C, Sorochinsky AE, Fustero S, Soloshonok VA, Liu H. Chem. Rev. 2014; 114: 2432
5c Zhou Y, Wang J, Gu Z, Wang S, Zhu W, Aceña JL, Soloshonok VA, Izawa K, Liu H. Chem. Rev. 2016; 116: 422

6 Xiong H.-Y, Pannecoucke X, Besset T. Chem. Eur. J. 2016; 22: 16734
7 Rico I, Wakselhan C. Tetrahedron Lett. 1981; 22: 323
8 Hansch C, Leo A, Taft RW. Chem. Rev. 1991; 91: 165
9 Zafrani Y, Yeffet D, Sod-Moriah G, Berliner A, Amir D, Marciano D, Gershonov E, Saphier S. J. Med. Chem. 2017; 60: 797
10 Ito M, Ishigami T. Infection 1991; 19: S253
11 Fourie JJ, Horak IG, de la Puente Redondo V. Vet. Rec. 2010; 167: 442
12 Jeanmart S, Edmunds AJ. F, Lamberth C, Pouliot M. Bioorg. Med. Chem. 2016; 24: 317
13 Yoshimura T, Ikeuchi T, Ohno S, Asakura S, Hamada Y. J. Pestic. Sci. 2013; 38: 171
14 Morita K, Ide K, Hayase Y, Takahashi T, Hayashi Y. Agric. Biol. Chem. 1987; 51: 1339
15 Wu J, Gu Y, Leng X, Shen Q. Angew. Chem. Int. Ed. 2015; 54: 7648

16a Bootwicha T, Liu X, Pluta R, Atodiresei I, Rueping M. Angew. Chem. Int. Ed. 2013; 52: 12856
16b Shao X, Xu C, Lu L, Shen Q. Acc. Chem. Res. 2015; 48: 1227

17 Zhu D, Gu Y, Lu L, Shen Q. J. Am. Chem. Soc. 2015; 137: 10547
18 Shen F, Zhang P, Lu L, Shen Q. Org. Lett. 2017; 19: 1032
19 Xu W, Ma J, Yuan X.-A, Dai J, Xie J, Zhu C. Angew. Chem. Int. Ed. 2018; 57: 10357

20a Roberts BP. Chem. Soc. Rev. 1999; 28: 25
20b Le C, Liang Y, Evans RW, Li X, MacMillan DW. C. Nature 2017; 547: 79

21a Ferry A, Billard T, Langlois BR, Bacqué E. J. Org. Chem. 2008; 73: 9362
21b Ferry A, Billard T, Langlois BR, Bacque E. Angew. Chem. Int. Ed. 2009; 48: 8551
21c Alazet S, Zimmer L, Billard T. Chem. Eur. J. 2014; 20: 8589

22 Ismalaj E, Le Bars D, Billard T. Angew. Chem. Int. Ed. 2016; 55: 4790
23 Xiong H.-Y, Bayle A, Pannecoucke X, Besset T. Angew. Chem. Int. Ed. 2016; 55: 13490
24 Huang Z, Matsubara O, Jia S, Tokunaga E, Shibata N. Org. Lett. 2017; 19: 934
25 Yan Q, Jiang L, Yi W, Liu Q, Zhang W. Adv. Synth. Catal. 2017; 359: 2471
26 Jiang L, Yi W, Liu Q. Adv. Synth. Catal. 2016; 358: 3700

27a Moore GG. I. J. Org. Chem. 1979; 44: 1708
27b Tang X.-J, Thomoson CS, Dolbier WR. Jr. Org. Lett. 2014; 16: 4594

28 Zhao X, Li T, Yang B, Qiu D, Lu K. Tetrahedron 2017; 73: 3112
29 Zhao X, Wei A, Li T, Su Z, Chen J, Lu K. Org. Chem. Front. 2017; 4: 232
30 Jiang L, Ding T, Yi W.-B, Zeng X, Zhang W. Org. Lett. 2018; 20: 2236
31 Jiang L, Yan Q, Wang R, Ding T, Yi W, Zhang W. Chem. Eur. J. 2018; 24: 18749

32a Zheng J, Wang L, Lin J.-H, Xiao J.-C, Liang SH. Angew. Chem. Int. Ed. 2015; 54: 13236
32b Zheng J, Cheng R, Lin J.-H, Yu DH, Ma L, Jia L, Zhang L, Wang L, Xiao J.-C, Liang SH. Angew. Chem. Int. Ed. 2017; 56: 3196
32c Luo J.-J, Zhang M, Lin J.-H, Xiao J.-C. J. Org. Chem. 2017; 82: 11206

33 Yu J, Lin J.-H, Xiao J.-C. Angew. Chem. Int. Ed. 2017; 56: 16669

34a Zheng J, Cai J, Lin J.-H, Guo Y, Xiao J.-C. Chem. Commun. 2013; 49: 7513
34b Zheng J, Lin J.-H, Cai J, Xiao J.-C. Chem. Eur. J. 2013; 19: 15261
34c Deng X.-Y, Lin J.-H, Zheng J, Xiao J.-C. Chem. Commun. 2015; 51: 8805

35 Zhu D, Shao X, Hong X, Lu L, Shen Q. Angew. Chem. Int. Ed. 2016; 55: 15807
36 Xu B, Wang D, Hu Y, Shen Q. Org. Chem. Front. 2018; 5: 1462
37 Larsson K, Rosenhall L. Clin. Exp. Allergy 1996; 26: 18
38 Xu B, Li D, Lu L, Wang D, Hu Y, Shen Q. Org. Chem. Front. 2018; 5: 2163
39 Guo S.-H, Zhang X.-L, Pan G.-F, Zhu X.-Q, Gao Y.-R, Wang Y.-Q. Angew. Chem. Int. Ed. 2018; 57: 1663

40a Wu X, Chu L, Qing FL. Angew. Chem. Int. Ed. 2013; 52: 2198
40b Mizuta S, Verhoog S, Engle KM, Khotavivattana T, O’Duill M, Wheelhouse K, Rassias G, Medebielle M, Gouverneur V. J. Am. Chem. Soc. 2013; 135: 2505
40c Lin Q.-Y, Xu X.-H, Zhang K, Qing F.-L. Angew. Chem. Int. Ed. 2016; 55: 1479
40d Meyer CF, Hell SM, Misale A, Trabanco AA, Gouverneur V. Angew. Chem. Int. Ed. 2019; 58: 8829
40e Wu W, Dai W, Ji X, Cao S. Org. Lett. 2016; 18: 2918

41 Shao X, Hong X, Lu L, Shen Q. Tetrahedron 2019; 75: 4156

42a Prier CK, Rankic DA, MacMillan DW. C. Chem. Rev. 2013; 113: 5322
42b Ravelli D, Protti S, Fagnoni M. Chem. Rev. 2016; 116: 9850

43 Li J, Zhu D, Lv L, Li C.-J. Chem. Sci. 2018; 9: 5781
44 Wang W, Zhang S, Zhao H, Wang S. Org. Biomol. Chem. 2018; 16: 8565
45 Li H, Cheng Z, Tung C.-H, Xu Z. ACS Catal. 2018; 8: 8237

46a Miyaura N, Suzuki A. Chem. Rev. 1995; 95: 2457
46b Hayashi T, Yamasaki K. Chem. Rev. 2003; 103: 2829
46c Candeias NR, Montalbano F, Cal PM. S. D, Gois PM. P. Chem. Rev. 2010; 110: 6169

47a Seiple IB, Su S, Rodriguez RA, Gianatassio R, Fujiwara Y, Sobel AL, Baran PS. J. Am. Chem. Soc. 2010; 132: 13194
47b Dickschat A, Studer A. Org. Lett. 2010; 12: 3972
47c Sorin G, Martinez Mallorquin R, Contie Y, Baralle A, Malacria M, Goddard J.-P, Fensterbank L. Angew. Chem. Int. Ed. 2010; 49: 8721
47d Huang H, Zhang G, Gong L, Zhang S, Chen Y. J. Am. Chem. Soc. 2014; 136: 2280

48 Liu W, Liu P, Lv L, Li C.-J. Angew. Chem. Int. Ed. 2018; 57: 13499
49 Candish L, Pitzer L, Gómez-Suárez A, Glorius F. Chem. Eur. J. 2016; 22: 4753
50 Gu Y, Leng X, Shen Q. Nat. Commun. 2014; 5: 5405
51 Wu J, Liu Y, Lu C, Shen Q. Chem. Sci. 2016; 7: 3757
52 Wu J, Lu C, Lu L, Shen Q. Chin. J. Chem. 2018; 36: 1031
53 Yang Y.-D, Azuma A, Tokunaga E, Yamasaki M, Shiro M, Shibata N. J. Am. Chem. Soc. 2013; 135: 8782
54 Arimori S, Matsubara O, Takada M, Shiro M, Shibata N. R. Soc. Open Sci. 2016; 3: 160102
55 Kondo H, Maeno M, Sasaki K, Guo M, Hashimoto M, Shiro M, Shibata N. Org. Lett. 2018; 20: 7044
56 Gondo S, Matsubara O, Chachignon H, Sumii Y, Cahard D, Shibata N. Molecules 2019; 24: 221