Rhodium-catalyzed enantioselective intermolecular C-H silylation of simple arenes: synergistic substituent effects overcome silane redistribution to enable synthesis of Si-stereogenic arylsilanes.

The non-directed intermolecular C-H bond silylation has manifested itself as a versatile tool for the synthesis of organosilicon compounds; however, the corresponding asymmetric transformations remain elusive, primarily due to the facile self-reactions of silane reactants. Herein, we disclose an efficient protocol that involves steric-hindrance-enabled, Rh-catalyzed enantioselective intermolecular C-H bond silylation of simple arenes to deliver a broad array of Si-stereogenic monohydrosilanes in good yields with excellent enantioselectivities (up to 99% ee), featuring readily available starting materials, simple synthetic operations and mild reaction conditions.