Synthesis of Non-C2-Symmetric Biaryldiols via Organo-Electro Catalyzed Aryl-Aryl Dehydrogenative Cross-Coupling.

Despite a few successful examples, controlling the enantioselectivity in the asymmetric synthesis of non-C₂-symmetric biaryldiols has long been challenging. To address the issues of enantioselectivity and regioselectivity, we introduced a novel organoelectrocatalytic strategy enabling asymmetric aryl-aryl dehydrogenative cross-coupling reactions. Using this approach, valuable non-C₂-symmetric biaryldiols were obtained in up to 95% yields and 97% enantiomeric excesses (ees), and these compounds could be further applied as versatile ligands in asymmetric reactions. Detailed mechanistic studies supported a sequential diradical cross-coupling followed by a central-to-axial chirality conversion pathway.