Selective nucleophilic α-C alkylation of phenols with alcohols via Ti=C_α intermediate on anatase TiO₂ surface

C-C bond forming reaction by alkylation of aryl rings is a main pillar of chemistry in the production of broad portfolios of chemical products. The dominant mechanism proceeds via electrophilic substitution of secondary and tertiary carbocations over acid catalysts, forming multiple aryl alkylation products non-selectively through all secondary and tertiary carbons in the alkyl chains but producing little α-C alkylation products because primary carbocations are poorly stable. Herein, we report that anatase TiO₂ (TiO₂-A) catalyzes nucleophilic α-C alkylation of phenols with alcohols in high selectivity to simply linear alkylphenols. Experimental and computational studies reveal the formation of Ti=C- bond with the α-carbon of the alkyl group at oxygen vacancies of the TiO₂-A surface. The subsequent α-C alkylation by selective substitution of phenol ortho-C-H bond is verified by deuterium exchanged substrate and DFT calculations.