Stereodivergent asymmetric synthesis of P-atropisomeric Si-stereogenic monohydrosilanes

Abstract

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.