Enantioselective Heterocoupling of 2-Naphthylamines with 2-Naphthol Derivatives via Cooperative Photoactivation and Chiral Vanadium(V) Catalysis

The photoactivated heterocoupling of 2-naphthylamines with 2-naphthols/3-phenanthrols under LED light irradiation in the presence of a mononuclear chiral vanadium complex was established. The protocol features high cross-coupling selectivity and atom economy, affording various 2-amino-2′-hydroxy-1,1′-binaphthyl (NOBIN) derivatives in up to 95% yields with 90:10 enantiomeric ratio using equimolar ratios of coupling partners. Mechanistic studies involving NMR, kinetics, and DFT calculations demonstrated that NOBINs are efficiently formed via radical–radical coupling, which is the cooperative coupling between a cation radical species from an electron donor–acceptor (EDA) complex of photoactivated 2-naphthylamines with singlet oxo-terminal O 2 and a radical species of 2-naphthols activated by a chiral vanadium catalyst. This work expands the scope of asymmetric transformations, enabling heterocoupling with various partners that are unreactive toward vanadium catalysts alone.