Enantioselective synthesis of acyclic monohydrosilanes by steric hindrance assisted C-H silylation.

Herein, a rhodium-catalyzed desymmetrization of dihydrosilanes with heterocyclic compounds via intermolecular dehydrogenative C-H silylation is developed. The strategy tolerates a variety of thianaphthene and thiophene derivatives, giving rise to a wide range of silicon-stereogenic acyclic monohydrosilanes. Several rare skeletons featuring bis-silicon-stereogenic centers were also designed to enhance the library's diversity further. Preliminary mechanistic studies reveal that the surrounding spatial environment of the Si-center plays a crucial role in enabling intermolecular C-H silylation preferentially.