Copper/TEMPO-catalyzed aerobic alcohol oxidation: Mechanistic assessment of different catalyst systems

Combinations of homogeneous Cu salts and 2,2,6,6-tetramethylpiperidine-N- oxyl (TEMPO) have emerged as practical and efficient catalysts for the aerobic oxidation of alcohols. Several closely related catalyst systems have been reported, which differ in the identity of the solvent, the presence of 2,2-bipyridine as a ligand, the identity of basic additives, and the oxidation state of the Cu source. These changes have a significant influence on the reaction rates, yields, and substrate scope. In this report, we probe the mechanistic basis for differences among four different Cu/TEMPO catalyst systems and elucidate the features that contribute to efficient oxidation of aliphatic alcohols.