Reversal of Enantioselectivity Approach to BINOLs via Single and Dual 2-Naphthol Activation Modes.

A mechanism-driven enantiodivergent approach to chiral 1,1'-bi-2-naphthols via catalytic asymmetric oxidative coupling of 2-naphthol derivatives is described for the first time. By utilizing 2-naphthol derivatives with low oxidation potential, the substrates were activated by either chiral mononuclear or dinuclear vanadium(V) catalyst to promote distinctively different asymmetric reaction pathways: single versus dual substrate activation mechanisms.