Synthesis of gem ‐Phosphorylsilylalkenes Bearing Si/Si,P‐Stereogenic Centers by Regio‐ and Enantio‐Selective Pd‐Catalyzed Hydrosilylation

ABSTRACT The catalytic asymmetric synthesis of chiral molecules containing both silicon‐ and phosphorus‐stereogenic centers represents a highly attractive yet underexplored domain in synthetic chemistry, largely due to the considerable challenge associated with the simultaneous control of two distinct stereogenic elements. Herein, we disclose a palladium‐catalyzed enantioselective hydrosilylation that enables the construction of a C(sp 2 )─Si bond, affording a regioselective route to gem ‐phosphorylsilylalkenes bearing contiguous Si‐ and P‐stereocenters. This transformation operates through a synergistic combination of desymmetrization of dihydrosilanes and diastereomeric resolution (DR) of unsymmetrical and racemic alkynylphosphoryl substrates, in which a diverse array of silicon‐stereogenic gem ‐phosphorylsilylalkenes and their structural analogues bearing additional P‐stereogenic centers in good yields and high enantioselectivities (up to 98:2 er). Furthermore, the synthetic utility of this methodology is underscored by the concise preparation of structurally diverse organosilicon frameworks. Mechanistic investigations, supported by density functional theory (DFT) calculations, have been performed to delineate the reaction pathway and rationalize the observed regio‐ and enantioselectivity.