Enantioselective Construction of Six- and Seven-Membered Triorgano-Substituted Silicon-Stereogenic Heterocycles

A rhodium-catalyzed enantioselective construction of six- and seven-membered triorgano-substituted silicon-stereogenic heterocycles is developed. This process undergoes a direct dehydrogenative C−H silylation, giving access to a wide range of novel triorgano-substituted silicon-stereogenic heterocycles in good to excellent yields and enantioselectivities, that significantly enlarged the chemical space of the silicon-centered chiral molecules. Further elaboration of the chiral monohydrosilane product delivered various corresponding tetraorgano-substituted silicon-stereogenic heterocycles without the loss of enantiopurity. These novel silicon-bridged heterocycles exhibit bright blue fluorescence, which would have potential application prospects in organic optoelectronic materials.