Bioinspired aerobic oxidation of alcohols with a bifunctional ligand based on bipyridine and TEMPO

Abstract

A novel bioinspired bifunctional ligand incorporating metal-binding site and stable free radical has been synthesized. The catalytic system obtained from the bifunctional ligand with copper(I) iodide in the presence of N-methylimidazole is highly efficient for the oxidation of a broad range of primary benzylic, allylic, alkynyl, aliphatic alcohols and secondary benzylic alcohols to the corresponding aldehydes and ketones in good to excellent yields. The catalyst system exhibits broad functional-group compatibility. The reaction is carried out in acetonitrile as solvent under air balloon at room temperature. The catalyst system features excellent activity for primary aliphatic alcohol oxidation and a high chemoselective oxidation of primary alcohols over the secondary alcohols. This oxidation process is readily amenable to larger-scale application. The interaction of the different components in the reaction mixtures was studied by UV-visible spectroscopy. The data indicated that Cu(I) existed throughout the reaction. A plausible mechanism of the catalytic cycle is proposed.