Sulfur-Mediated Reactions through Sulfonium Salts and Ylides

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

Key words

sulfur - sulfonium salts - ylides - alkenes - alkynes - C–H functionalization - asymmetric catalysis

Publication History

Received: 28 January 2021

Accepted after revision: 05 March 2021

Accepted Manuscript online:
05 March 2021

Article published online:
23 March 2021

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