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

Abstract 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.