Synthesis of Non<i>-C</i>₂‑SymmetricBiaryldiols via Organo-Electro Catalyzed Aryl–Aryl DehydrogenativeCross-Coupling

Despite a few successful examples, controlling the enantioselectivity in the asymmetric synthesis of non-<i>C</i>₂-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-<i>C</i>₂-symmetric biaryldiols were obtained in up to 95% yields and 97% enantiomeric excesses (<i>ee</i>s), 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.