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Updated: Jun 15, 2025

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Dirhodium(II)/XantPhos Catalyzed Synthesis of β-(E)-Vinylsilanes via Hydrosilylation and Isomerization from Alkynes
Liqun Yang1, Mingjun Yi1, Xiaoyu Wu1
1Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240, China.
Abstract:
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.
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