Enantioselective Silylation of Aliphatic C−H Bonds for the Synthesis of Silicon‐Stereogenic Dihydrobenzosiloles

A rhodium(I)‐catalyzed enantioselective silylation of aliphatic C−H bonds for the synthesis of silicon‐stereogenic dihydrobenzosiloles is demonstrated. This reaction involves a highly enantioselective intramolecular C(sp 3 )−H silylation of dihydrosilanes, followed by a stereospecific intermolecular alkene hydrosilylation leading to the asymmetrically tetrasubstituted silanes. A wide range of dihydrosilanes and alkenes displaying various functional groups are compatible with this process, giving access to a variety of highly functionalized silicon‐stereogenic dihydrobenzosiloles in good to excellent yields and enantioselectivities.