title: A TEMPO-free copper-catalyzed aerobic oxidation of alcohols.
abstract: The copper-catalyzed aerobic oxidation of primary and secondary alcohols without an external N-oxide co-oxidant is described. The catalyst system is composed of a Cu/diamine complex inspired by the enzyme tyrosinase, along with dimethylaminopyridine (DMAP) or N-methylimidazole (NMI). The Cu catalyst system works without 2,2,6,6-tetramethyl-l-piperidinoxyl (TEMPO) at ambient pressure and temperature, and displays activity for un-activated secondary alcohols, which remain a challenging substrate for catalytic aerobic systems. Our work underscores the importance of finding alternative mechanistic pathways for alcohol oxidation, which complement Cu/TEMPO systems, and demonstrate, in this case, a preference for the oxidation of activated secondary over primary alcohols.
authors: Department of Chemistry, McGill University, 801 Sherbrooke St. West Montreal, Quebec, H3A 0B8 (Canada).
authors: Boran
authors: B
authors: Xu
authors: Jean-Philip
authors: JP
authors: Lumb
authors: Bruce A
authors: BA
authors: Arndtsen
mesh_terms: D000332:Aerobiosis; D000438:Alcohols / Q000737:chemistry*; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D003497:Cyclic N-Oxides / Q000737:chemistry*
chemical_list: D000438:Alcohols; D003497:Cyclic N-Oxides; D003300:Copper; C003959:TEMPO
keywords: aerobic oxidation; alcohols; biomimetic catalysis; copper; tyrosinase