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

A unique transition-metal-free radical thiolation of2-azaallylanions has been developed. Easily accessible thiosulfonates and 2-azaallylsundergo the tandem process of single-electron transfer and radical-radicalcoupling to construct C-(sp(3))-S bonds. This robustprotocol enables a mild and chemoselective coupling between 2-azaallylanions and thiosulfonates to access alpha-amino sulfides in 50-92%yields (25 examples). The scalability of this protocol was demonstratedby telescopic gram-scale experiments. Mechanistic studies providesignificant evidence for this radical thiolation reaction.

Automated summary

A unique transition-metal-free radical thiolation of 2-azaallylanions has been developed. This robust protocol enables the mild and chemoselective coupling between 2-azaallylanions and thiosulfonates to access alpha-amino sulfides. Mechanistic studies provide significant evidence for this radical thiolation reaction.