Construction of functionalized adjacent P(<scp>v</scp>)–C chiral stereogenic centers <i>via</i> organophosphine-catalyzed asymmetric S_N2′ substitution of unsymmetrical phosphine oxides with MBH adducts

Phosphorus(V) stereogenic centers are prevalent in various pharmaceuticals, pesticides, and functional materials. Herein, we report an organophosphine-catalyzed asymmetric S_N2' substitution between unsymmetrical phosphine oxides and Morita-Baylis-Hillman adducts through an umpolung addition pathway, allowing the efficient construction of functionalized adjacent P(V)-C chiral stereogenic centers. A chiral phosphine catalyst, derived from an amino acid, enabled the formation of the desired products in high yields (up to 99%) and excellent enantioselectivities (up to 97% ee). This method demonstrates broad substrate scope, and the products can be easily diversified into valuable derivatives.