Synlett 2021; 32(13): 1275-1280
DOI: 10.1055/a-1409-0906
cluster account
Perspectives on Organoheteroatom and Organometallic Chemistry

Sulfur-Mediated Reactions through Sulfonium Salts and Ylides

Pingfan Li
I would like to thank the National Natural Science Foundation of China (21402005), the Natural Science Foundation of Beijing Municipality (2202040), and the Beijing University of Chemical Technology for financial support.


Abstract

This Account discusses several new reaction methods developed in our group that utilize sulfur-mediated reactions through sulfonium salts and ylides, highlighting the interplay of rational design and serendipity. Our initial goal was to convert aliphatic C–H bonds into C–C bonds site-selectively, and without the use of transition-metal catalysts. While a proof-of-concept has been achieved, this target is far from being ideally realized. The unexpected discovery of an anti-Markovnikov rearrangement and subsequent studies on difunctionalization of alkynes were much more straightforward, and eventually led to the new possibility of asymmetric N–H insertion of sulfonium ylides through Brønsted acid catalysis.

1 Introduction

2 Allylic/Propargylic C–H Functionalization

3 Anti-Markovnikov Rearrangement

4 Difunctionalization of Alkynes

5 Asymmetric N–H Insertion of Sulfonium Ylides

6 Conclusion



Publication History

Received: 28 January 2021

Accepted after revision: 05 March 2021

Accepted Manuscript online:
05 March 2021

Article published online:
23 March 2021

© 2021. Thieme. All rights reserved

Georg Thieme Verlag KG
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  • References

    • 1a Pulis AP, Procter DJ. Angew. Chem. Int. Ed. 2016; 55: 9842
    • 1b Yorimitsu H. Chem. Rec. 2017; 17: 1156
    • 1c Kaiser D, Klose I, Oost R, Neuhaus J, Maulide N. Chem. Rev. 2019; 119: 8701
    • 1d Wang N, Saidhareddy P, Jiang X. Nat. Prod. Rep. 2020; 37: 246
    • 1e Fan R, Tan C, Liu Y, Wei Y, Zhao X, Liu X, Tan J, Yoshida H. Chin. Chem. Lett. 2021; 32: 299
  • 2 Peese KM, Gin DY. J. Am. Chem. Soc. 2006; 128: 8734
  • 3 McKerrall SJ, Jørgensen L, Kuttruff CA, Ungeheuer F, Baran PS. J. Am. Chem. Soc. 2014; 136: 5799
  • 4 Singleton DA, Hang C. J. Org. Chem. 2000; 65: 7554
    • 5a Sharpless KB, Hori T, Truesdale LK, Dietrich CO. J. Am. Chem. Soc. 1976; 98: 269
    • 5b Sharpless KB, Hori T. J. Org. Chem. 1976; 41: 176
    • 5c Bruncko M, Khuong T.-AV, Sharpless KB. Angew. Chem. Int. Ed. 1996; 35: 454
    • 6a Snider BB, Hrib NJ, Fuzesi L. J. Am. Chem. Soc. 1976; 98: 7115
    • 6b Snider BB, Füzesi L. Tetrahedron Lett. 1978; 19: 877
  • 7 Veselovsky VV, Dragan VA, Moiseenkov AM. Tetrahedron Lett. 1988; 29: 6637
  • 8 Hu G, Xu J, Li P. Org. Lett. 2016; 18: 887
    • 9a MacMillan DW. C. Nature 2008; 455: 304
    • 9b Crabtree RH, Lei A. Chem. Rev. 2017; 117: 8481
  • 10 Hu G, Xu J, Li P. Org. Lett. 2014; 16: 6036
  • 11 Hu G, Xu J, Li P. Org. Chem. Front. 2018; 5: 2167
    • 12a Wang Y, Zhu J, Durham AC, Lindberg H, Wang Y.-M. J. Am. Chem. Soc. 2019; 141: 19594
    • 12b Wang Y, Zhu J, Guo R, Lindberg H, Wang Y.-M. Chem. Sci. 2020; 11: 12316
    • 12c Fernández-Salas JA, Eberhart AJ, Procter DJ. J. Am. Chem. Soc. 2016; 138: 790
    • 13a Hu G, Xu J, Li P. Org. Biomol. Chem. 2018; 16: 4151
    • 13b Huang J, Hu G, An S, Chen D, Li M, Li P. J. Org. Chem. 2019; 84: 9758
    • 14a Fernández-Salas JA, Pulis AP, Procter DJ. Chem. Commun. 2016; 52: 12364
    • 14b Shi Y, Li P. Tetrahedron Lett. 2018; 59: 3104
  • 15 He Z, Song F, Sun H, Huang Y. J. Am. Chem. Soc. 2018; 140: 2693
  • 16 Luo H, Hu G, Li P. J. Org. Chem. 2019; 84: 10569
  • 17 Zhang Z, Du H, Xu J, Li P. Chem. Commun. 2016; 52: 11547
  • 18 Yamanaka H, Matsuo J, Kawana A, Mukaiyama T. Chem. Lett. 2003; 32: 626
  • 19 Zhang Z, Li P. Tetrahedron Lett. 2020; 61: 151707
  • 20 Zhang Z, Luo Y, Du H, Xu J, Li P. Chem. Sci. 2019; 10: 5156
  • 21 Zhang Z, He P, Du H, Xu J, Li P. J. Org. Chem. 2019; 84: 4517
  • 22 da Silva Gomes R, Corey EJ. J. Am. Chem. Soc. 2019; 141: 20058
  • 24 Ren Y.-Y, Zhu S.-F, Zhou Q.-L. Org. Biomol. Chem. 2018; 16: 3087
  • 25 Guo W, Luo Y, Sung HH. Y, Williams ID, Li P, Sun J. J. Am. Chem. Soc. 2020; 142: 14384
  • 26 Momo PB, Leveille AN, Farrar EH. E, Grayson MN, Mattson AE, Burtoloso AC. B. Angew. Chem. Int. Ed. 2020; 59: 15554