Catalytic Enantioselective Synthesis of Silicon-Stereogenic Alkoxysilanes and Siloxanes

A Rh-catalyzed enantioselective intermolecular dehydrogenative Si−O coupling of dihydrosilanes with alocohols and silanols is demonstrated. Rh(I) catalyst equipped with a Josiphos ligand enables the highly enantioselective alcoholysis process of dihydrosilanes, giving access to a variety of functionalized triorgano-substituted silicon-stereogenic alkoxysilanes and siloxanes in decent yields and ee, which significantly expand the chemical space of the silicon-centered chiral molecules. Utility of this methodology is illustrated by the construction of CPL-active (circularly polarized luminescence) chiral alkoxysilane small organic molecules.

Novel amide-functionalized chloramphenicol base bifunctional organocatalysts for enantioselective alcoholysis of meso-cyclic anhydrides

A family of novel chloramphenicol base-amide organocatalysts possessing a NH functionality at C-1 position as monodentate hydrogen bond donor were developed and evaluated for enantioselective organocatalytic alcoholysis of meso-cyclic anhydrides. These structural diversified organocatalysts were found to induce high enantioselectivity in alcoholysis of anhydrides and was successfully applied to the asymmetric synthesis of (S)-GABOB.