Electrochemical Oxidation of Benzyl Alcohols via Hydrogen Atom Transfer Mediated by 2,2,2-Trifluoroethanol

We report a novel electrochemical oxidation of benzyl alcohols. We found that trifluoroethanol plays a role as a hydrogen atom transfer (HAT) mediator, enabling the oxidation of electron-deficient substrates that are difficult to directly oxidize on electrode surfaces. Density-functional theory calculations, cyclic voltammetry measurements and constant potential electrolysis studies supported the proposed HAT mechanism. Moreover, the obtained carbonyl compounds could be functionalized in an electro-chemically one-pot manner, further highlighting their synthetic utility.