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, nitrile, amines, esters, and heterocycles.