Cu(I) Catalyzed Germyl S‐Phosphorothiolation of Electron‐Deficient Alkene

A copper‐catalyzed three‐component radical relay protocol is demonstrated for difunctionalization of electron‐withdrawing alkenes using germanium hydride and S ‐phosphorothiol to afford the germylphosphorothiolated product. This transformation reveals excellent tolerance for functional groups and occurs under mild reaction conditions, exhibiting a high level of regioselectivity. Control experiments suggest the involvement of germyl radicals in these transformations.