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
