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

ABSTRACT 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.