Highly Enantioselective Construction of Multifunctional Silicon‐Stereogenic Silacycles by Asymmetric Enamine Catalysis

Abstract We report the first highly enantioselective construction of silicon‐stereocenters by asymmetric enamine catalysis. An unprecedented desymmetric intramolecular aldolization of prochiral siladials was thus developed for the facile access of multifunctional silicon‐stereogenic silacycles in high to excellent enantioselectivity. With an enal moiety, these adducts could be readily elaborated for the diverse synthesis of silicon‐stereogenic compounds, and for late‐stage modification.