Radical C(sp3)-S Coupling for the Synthesis of alpha-Amino Sulfides

By:Duan, Shengzu; Zi, Yujin; Du, Ya; Cong, Jielun; Sun, Xiaotong; Jing, Hong; Zhao, Jingfeng; Chen, Wen; Yang, Xiaodong

Organic Letters

DOI：https://doi.org/10.1021/acs.orglett.3c01121

Published：2023-May-26

Abstract

A unique transition-metal-free radical thiolation of 2-azaallyl anions has been developed. Easily accessible thiosulfonates and 2-azaallyls undergo the tandem process of single-electron transfer and radical-radical coupling to construct C(sp3)-S bonds. This robust protocol enables a mild and chemoselective coupling between 2-azaallyl anions and thiosulfonates to access alpha-amino sulfides in 50-92% yields (25 examples). The scalability of this protocol was demonstrated by telescopic gram-scale experiments. Mechanistic studies provide significant evidence for this radical thiolation reaction.