Catalytic Kinetic Resolution of Monohydrosilanes via Rhodium‐Catalyzed Enantioselective Intramolecular Hydrosilylation

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The catalytic access of silicon‐stereogenic organosilanes remains a big challenge, and largely depends on the desymmetrization of the symmetric precursors with two identical substitutes attached to silicon atom. Here we report the construction of silicon‐stereogenic organosilanes via catalytic kinetic resolution of racemic monohydrosilanes with good to excellent selectivity factors. Both Si‐stereogenic dihydrobenzosiloles and Si‐stereogenic monohydrosilanes could be efficiently accessed in one single operation via Rh‐catalyzed enantioselective intramolecular hydrosilylation, employing ( R,R )‐Et‐DuPhos as the optimal ligand. This catalytic protocol features mild conditions, a low catalyst loading (0.1 mol % [Rh(cod)Cl] 2 ), high stereoinduction ( S factor up to 152), and excellent scalability. Moreover, further derivatizations led to the efficient synthesis of uncommon middle‐size (7‐ and 8‐membered) Si‐stereogenic silacycles. Preliminary mechanistic study indicates this reaction might undergo a modified Chalk–Harrod mechanism.