Highly β( Z)-Selective Hydrosilylation of Terminal Alkynes Catalyzed by Thiolate-Bridged Dirhodium Complexes.
Xiangyu ZhaoDawei YangYahui ZhangBaomin WangJingping QuPublished in: Organic letters (2018)
A series of novel monothiolate-bridged dirhodium complexes, [Cp*Rh(μ-SR)(μ-Cl)2RhCp*][BF4] {Cp* = η5-C5Me5, R = tertiary butyl ( tBu), 1a; R = ferrocenyl (Fc), 1b; R = adamantyl (Ad), 1c} were designed and successfully synthesized, which can smoothly facilitate highly regioselective and stereoselective hydrosilylation of terminal alkynes to afford β( Z) vinylsilanes with good functional group compatibility. Furthermore, the hydride bridged dirhodium complex [Cp*Rh(μ-S tBu)(μ-Cl)(μ-H)RhCp*][BF4] (5) as a potential intermediate was obtained by the reaction of 1a with excess HSiEt3.