Catalytic Asymmetric Synthesis of Silicon‐Stereogenic Dihydrodibenzosilines: Silicon Central‐to‐Axial Chirality Relay

Abstract A Rh‐catalyzed asymmetric synthesis of silicon‐stereogenic dihydrodibenzosilines featuring axially chiral 6‐membered bridged biaryls is demonstrated. In the presence of a Rh I catalyst with a chiral diphosphine ligand, a wide range of dihydrodibenzosilines containing both silicon‐central and axial chiralities are conveniently constructed in excellent enantioselectivities via dehydrogenative C(sp 3 )−H silylation. Absolute configuration analysis by single‐crystal X‐ray structures revealed a novel silicon central‐to‐axial chirality relay phenomenon, which we believe will inspire further research in the field of asymmetric catalysis and chiroptical materials.