Dirhodium(II)/XantPhos Catalyzed Synthesis of β‐(E)‐Vinylsilanes via Hydrosilylation and Isomerization from Alkynes

A concise hydrosilylation of alkynes for synthesizing β-(E)-vinylsilanes catalyzed by dirhodium(II)/XantPhos has been developed. In this reaction, β-(E)-vinylsilanes were generated from the isomerization of β-(Z)-vinylsilanes catalyzed by dirhodium(II) hydride species rather than the direct insertion of triple bond into M-H or M-Si bond (traditional Chalk-Harrod mechanism or modified Chalk-Harrod mechanism). The hydrosilylation displayed a broad substrate scope for alkynes and tertiary silanes, tolerating diverse functional groups including halides, nitriles, amines, esters, and heterocycles.