Thioamide‐Directed Transition‐metal‐catalyzed C(sp2) –H bond vinylation and arylation of Ferrocenes

Thioamide-chelation-assisted direct Rh(III)-catalyzed C-H vinylation and Ir(III)-catalyzed C-H arylation of ferrocenes with vinyl- or aryltrimethoxysilane under mild and base-free conditions is described. With thioamide as directing group, various monovinyl and monoaryl substituted thioamideferrocenes were obtained by transition metal-catalyzed direct C-H functionalization of ferrocenes in 50%-84% yields with broad substrate range. Mechanistic experiments indicate that C-H bond activation may be the rate-determining step of the reaction.