Catalytic Enantioselective Dehydrogenative Si-O Coupling to Access Chiroptical Silicon-Stereogenic Siloxanes and Alkoxysilanes

A rhodium-catalyzed enantioselective construction of triorgano-substituted silicon-stereogenic siloxanes and alkoxysilanes is developed. This process undergoes a direct intermolecular dehydrogenative Si-O coupling between dihydrosilanes with silanols or alocohols, giving access to a variety of highly functionalized chiral siloxanes and alkoxysilanes in decent yields with excellent stereocontrol, that significantly expand the chemical space of the silicon-centered chiral molecules. Further utility of this process was illustrated by the construction of CPL-active (circularly polarized luminescence) silicon-stereogenic alkoxysilane small organic molecules. Optically pure bis-alkoxysilane containing two silicon-stereogenic centers and three pyrene groups displayed a remarkable glum value with a high fluorescence quantum efficiency (g(lum) = 0.011, Phi(F) = 0.55), which could have great potential application prospects in chiral organic optoelectronic materials.

Automated summary

A rhodium-catalyzed enantioselective construction of triorgano-substituted silicon-stereogenic siloxanes and alkoxysilanes has been developed, expanding the chemical space of silicon-centered chiral molecules. The method was further demonstrated by constructing CPL-active silicon-stereogenic alkoxysilane small organic molecules with potential applications in chiral organic optoelectronic materials.