Highly efficient and general Ir-catalyzed hydrosilylation of unactivated alkenes with excellent anti-Markovnikov regioselectivity was described. A broad scope of hydrosilylated products were synthesized economically and conveniently from commercially or naturally available compounds, which provides versatile valuable precursors for organic and medicinal studies.

Developing efficient strategies for Markovnikov hydrosilylation of alkynes is still an important goal. The steric and electronic properties of hydrosilanes are key factors in controlling selectivity in these reactions. Here by using a trimethylsilyl-protected trihydroxysilane, we report a mild, efficient strategy for Markovnikov hydrosilylation of terminal alkynes with the simple catalyst [Ir(μ-Cl)(cod)] 2 . A variety of terminal alkynes are hydrosilylated efficiently with outstanding α-regioselectivity. This protocol is successfully utilized in the late-stage hydrosilylation of derivatives of various bio-relevant molecules. The residual silyl group, -Si (OSiMe 3 ) 3 , can participate in organic transformations directly, or be converted into other useful silyl groups.

One mild and simple Ir/hydrosilane catalytic system for isomerization of 2-substituted allylic ethers with high specificity and chemoselectivity was developed.

One direct and efficient procedure for the synthesis of 1,1-disilylated terminal alkenes is demonstrated.