Nickel-Catalyzed Regiodivergent and Enantioselective Hydrosilylation of Internal Alkenes

Enantioselective hydrosilylation of alkenes represents a direct and economical route to chiral organosilanes. However, achieving good regio- and enantioselectivity from the same alkene for the divergent synthesis of chiral silanes remains a formidable challenge, particularly for internal alkenes. In this work, we present a ligand-controlled nickel-catalyzed regiodivergent and enantioselective hydrosilylation of 1,2-disubstituted alkenes. This approach provides a direct access to both α- and β-trifluoromethylsilanes with high regio- and enantioselectivity. The resulting enantioenriched silane products are amenable to various stereospecific transformations. Moreover, density functional theory (DFT) calculations elucidate the origin of the observed regio- and enantioselectivity.