Construction of Chiral Tetraorganosilicons by Tandem Desymmetrization of Silacyclobutanes/Intermolecular Dehydrogenative Silylation

We report a method to construct chiral tetraorganosilicons by tandem silacyclobutane (SCB) desymmetrization–dehydrogenative silylations. A wide array of dibenzosiloles with stereogenic quaternary silicon centers were obtained in good yields and enantioselectivities up to 93 % ee . Chiral TMS‐segphos was found to be a superior ligand in terms of reactivity and enantioselectivity.