Synthesis of Si‐Stereogenic Silanols by Catalytic Asymmetric Hydrolytic Oxidation

Abstract Despite growing progress in the construction of chiral organosilicon compounds, the catalytic asymmetric synthesis of silicon‐stereogenic silanols is less explored and remains a considerable challenge. Herein, we report the first enantioselective construction of silicon‐stereogenic silanols by the catalytic asymmetric hydrolytic oxidation of dihydrosilanes. This practical procedure features ambient reaction conditions, high atom economy, good functional‐group compatibility, and H 2 as the only by‐product, and produces a wide range of valuable chiral silanols and bis‐silanols in decent yields with excellent chemo‐ and stereoselectivity.