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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).
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