Copper‐Catalyzed Enantioselective C–H Phosphorylation Enabled by a 3,3’‐Difluorinated BINOL Ligand

The asymmetric construction of C-P bonds via transition-metal-catalyzed enantioselective C-H activation remains a significant and unresolved challenge. Herein, we report an unprecedented copper-catalyzed enantioselective C-H phosphorylation through oxidative C-H/P-H coupling. This method employs earth-abundant copper catalyst and readily accessible 3,3'-difluorinated BINOL (1,1'-bi-2-naphthol) ligand, which proved essential for achieving high reactivity and enantioselectivity. A broad range of unmasked H-phosphonates and secondary phosphine oxides (SPOs) serve as practical coupling partners, delivering planar-chiral metallocenes in good yields with high enantioselectivity (up to 99:1 er). The robustness of this approach is demonstrated through gram-scale synthesis, facile directing-group removal, and versatile downstream transformations. Furthermore, the resulting chiral phosphines were applied as a new class of Lewis base catalysts in the enantioselective allylation of aldehydes, underscoring their potential utility in asymmetric synthesis.