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.

Automated summary

In this study, a rhodium-catalyzed desymmetrization of dihydrosilanes with heterocyclic compounds via intermolecular dehydrogenative C-H silylation was developed. The strategy demonstrated tolerance towards a variety of thianaphthene and thiophene derivatives, leading to the synthesis of a wide range of silicon-stereogenic acyclic monohydrosilanes. Additionally, rare skeletons featuring bis-silicon-stereogenic centers were designed to further enhance the diversity of the compound library. Preliminary mechanistic studies revealed the crucial role of the spatial environment surrounding the Si-center in enabling intermolecular C-H silylation preferentially.