Visible-Light-Catalyzed Carboxylation of CO2 with the C(sp3)–O Bond of Benzyl Alcohol

Abstract A visible-light-catalyzed direct carboxylation of the benzylic C(sp3)–O bond with CO2 has been developed. This strategy employs triphenylsilane (Ph3SiH) as both a reductive quencher and an in situ alcohol activator, enabling the direct carboxylation of free benzylic alcohols without the need for pre-functionalization, thereby significantly improving the step economy. The catalytic system efficiently converts primary, secondary, and even highly sterically hindered tertiary benzylic alcohols and has been successfully applied to the synthesis of pharmaceutical molecules.