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Copper-Catalyzed Aerobic Oxidative Functionalization of an Arene C−H Bond: Evidence for an Aryl-Copper(III) Intermediate

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journal contribution
posted on 01.09.2010, 00:00 by Amanda E. King, Lauren M. Huffman, Alicia Casitas, Miquel Costas, Xavi Ribas, Shannon S. Stahl
Recent studies have highlighted the ability of CuII to catalyze the aerobic oxidative functionalization of C−H bonds; however, very little is known about the mechanisms of these reactions. Here, we describe the CuII-catalyzed C−H methoxylation and amidation of a macrocylic arene substrate with O2 as the stoichiometric oxidant. Kinetic and in situ spectroscopic studies demonstrate the involvement of three different oxidation states of Cu in the catalytic mechanism, including an aryl-CuIII intermediate. These observations establish a novel mechanistic pathway that has implications for numerous other Cu-catalyzed aerobic oxidation reactions.