[2,3]-Sigmatropic Rearrangement of Arylhydroxylamines: Rapid Access to ortho-Sulfonylated Anilines

Abstract

In the absence of transition-metal catalysts and additional oxidants, arylhydroxylamines can undergo an unconventional O-sulfinylation/[2,3]-sigmatropic rearrangement/rearomatization cascade with trifluoromethylsulfinyl chloride to rapidly and efficiently synthesize versatile ortho-sulfonylated aromatic amines. This Synpacts article describes the discovery, further study, and practical application of the rearrangement reactions in arylhydroxylamine compounds and highlights our recent advances in this area.

1 Introduction

2 Discovery of a New Reaction

3 O-Sulfinylation of Arylhydroxylamines Followed by [2,3]-σ Rearrangement

4 Conclusion

Key words

arylhydroxylamines - ortho-sulfonylated anilines - sigmatropic rearrangement - trifluoromethanesulfonylation - DFT calculation

• References

• 1 Tabolin AA, Ioffe SL. Chem. Rev. 2014; 114: 5426
• 2 Bamberger E. Ber. Dtsch. Chem. Ges. 1894; 27: 1548
• 3a Kouznetsov VV, Zubkov FI, Nikitina EV, Duarte LD. A. Tetrahedron Lett. 2004; 45: 1981
• 3b Hojczyk KN, Feng P, Zhan C, Ngai MY. Angew. Chem. Int. Ed. 2014; 53: 14559
• 3c Nakamura I, Jo T, Ishida Y, Tashiro H, Terada M. Org. Lett. 2017; 19: 3059
• 4a Behrman EJ. Beilstein J. Org. Chem. 2006; 2: No. 22
• 4b Wang Y, Liu L, Zhang L. Chem. Sci. 2013; 4: 739
• 4c Wang H.-Y, Anderson LL. Org. Lett. 2013; 15: 3362
• 4d Yuan H, Guo L, Liu F, Miao Z, Feng L, Gao H. ACS Catal. 2019; 9: 3906
• 5 Porzelle A, Woodrow MD, Tomkinson NC. O. Org. Lett. 2010; 12: 1492
• 6 Xiong F, Lu L, Sun T.-Y, Wu Q, Yan D, Chen Y, Zhang X, Wei W, Lu Y, Sun W.-Y, Li JJ, Zhao J. Nat. Commun. 2017; 8: 15912
• 7 Xiong F, Zuo Y, Song Y, Zhang L, Zhang X, Xu S, Ren Y. Org. Lett. 2020; 22: 3799
• 8a Guo L, Liu F, Wang L, Yuan H, Feng L, Kurti L, Gao H. Org. Lett. 2019; 21: 2894
• 8b Guo L, Liu F, Wang L, Yuan H, Feng L, Lu H, Gao H. Org. Chem. Front. 2020; 7: 1077
• 8c Yuan H, Du Y, Liu F, Guo L, Sun Q, Feng L, Gao H. Chem. Commun. 2020; 56: 8226
• 8d Wang M, Liu Y, Wang L, Lu H, Feng L, Gao H. Adv. Synth. Catal. 2021; 363: 1733
• 9a Zhang Z, Luo J, Gao H. Org. Lett. 2021; 23: 9332
• 9b Du Y, Xi Z, Guo L, Lu H, Feng L, Gao H. Tetrahedron Lett. 2021; 72: 153074
• 10 Liu Y, Bai S, Du Y, Qi X, Gao H. Angew. Chem. Int. Ed. 2022; 61: e202115611
• 11 Chatelain P, Sau A, Rowley CN, Moran J. Angew. Chem. Int. Ed. 2019; 58: 14959
• 12 Steensma RW, Galabi S, Tagat JR, McCombie SW. Tetrahedron Lett. 2001; 42: 2281
• 13 Watanabe T, Ueda S, Inuki S, Oishi S, Fujii N, Ohno H. Chem. Commun. 2007; 4516