title: Highly Regio- and Stereoselective Hydrosilylation of Internal Thioalkynes under Mild Conditions.
abstract: 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.
authors.affiliation: Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong SAR (China).
authors.forename: Shengtao
authors.initials: S
authors.lastname: Ding
authors.forename: Li-Juan
authors.initials: LJ
authors.lastname: Song
authors.forename: Yong
authors.initials: Y
authors.lastname: Wang
authors.forename: Xinhao
authors.initials: X
authors.lastname: Zhang
authors.forename: Lung Wa
authors.initials: LW
authors.lastname: Chung
authors.forename: Yun-Dong
authors.initials: YD
authors.lastname: Wu
authors.forename: Jianwei
authors.initials: J
authors.lastname: Sun
keywords: electron-rich alkynes; homogeneous catalysis; hydrosilylation; ruthenium; stereoselectivity