Copper‐Catalyzed Phosphorus Radical Transformations for the Assembly of P‐Stereogenic Architectures

Phosphorus-centered radicals hold transformative potential for organophosphorus synthesis, yet their configurational lability and distinctive reactivity profiles have historically restricted their application in asymmetric catalysis. Herein, we report a copper-photoredox catalytic system that enables the stereoselective generation of copper-bound P-centered radicals and their subequent stereoretentive transformations within a well-defined chiral environment. The synergistic approach achieves unprecedented kinetic resolutions of racemic H-phosphinates with α-trifluoromethyl styrenes or gem-difluorostyrenes, delivering 85 fluorine-containing P-chiral phosphinates with up to 98% ee. The method thereby bridges a synthetic gap for these previously inaccessible, pharmacologically significant compounds. Mechanistic and computational studies reveal a stereochemical relay: enantiodiscriminatory binding of racemic substrates, photoinduced ligand-to-metal charge transfer (LMCT) for radical generation, and stereoretentive bond formation. By reconciling radical reactivity with stereochemical fidelity, our strategy establishes metallaphotoredox catalysis as a versatile paradigm for heteroatom-centered stereochemistry.