Highly Regio- and Stereoselective Hydrosilylation of Internal Thioalkynes under Mild Conditions

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 a 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.