Stereodivergent asymmetric synthesis of P-atropisomeric Si-stereogenic monohydrosilanes

Silicon-stereogenic monohydrosilanes, with an operative Si-H bond, have attracted increasing interest due to their broad applications in synthetic chemistry, medicinal chemistry, and materials science. Phosphine compounds, with their versatile ligating properties, occupy a central position in modern transition metal catalysis. Despite both types of compounds being of great importance, the marriage of silicon-stereogenic monohydrosilanes with phosphines is rare, namely, access to enantioenriched phosphine-based silicon-stereogenic monohydrosilanes remains significantly challenging. Here we present an efficient one-pot strategy for the stereodivergent asymmetric synthesis of various P-atropisomeric Si-stereogenic monohydrosilanes with excellent stereoselectivity. Key to this is a desymmetric substitution between chiral phosphine nucleophiles and dichloro-monohydrosilanes with axial-to-silicon-central transfer of chirality, followed by a stereospecific transformation. This one-pot process sets an effective platform for ready access to P-atropisomeric Si-stereogenic monohydrosilanes, which could have potential applications in asymmetric catalysis. We herein report an efficient one-pot strategy for the stereodivergent asymmetric synthesis of various P-atropisomeric Si-stereogenic monohydrosilanes with excellent stereoselectivity from dichlorosilanes.