Radical C(sp 3 )-S Coupling for the Synthesis of α-Amino Sulfides.

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(sp 3 )-S bonds. This robust protocol enables a mild and chemoselective coupling between 2-azaallyl anions and thiosulfonates to access α-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.