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A general and mild hydrosilylation of thioalkynes is described. With the cationic catalyst Cp*Ru(MeCN)3 (+) and the bulky silane (TMSO)3 SiH, a range of thioalkynes underwent smooth hydrosilylation at room temperature with excellent α regioselectivity and syn stereoselectivity. DFT calculations provided important insight into the mechanism, particularly the unusual syn selectivity with the Cp*Ru(MeCN)3 (+) catalyst. The sulfenyl group in the substrates was found to provide important chelation stabilization to direct the reaction through a new mechanistic pathway.
Ding et al. (Tue,) studied this question.