title: Copper-catalyzed aerobic oxidative functionalization of an arene C-H bond: evidence for an aryl-copper(III) intermediate.
abstract: Recent studies have highlighted the ability of Cu(II) 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 Cu(II)-catalyzed C-H methoxylation and amidation of a macrocylic arene substrate with O(2) 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-Cu(III) intermediate. These observations establish a novel mechanistic pathway that has implications for numerous other Cu-catalyzed aerobic oxidation reactions.
authors.affiliation: Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53704, USA.
authors.forename: Amanda E
authors.initials: AE
authors.lastname: King
authors.forename: Lauren M
authors.initials: LM
authors.lastname: Huffman
authors.forename: Alicia
authors.initials: A
authors.lastname: Casitas
authors.forename: Miquel
authors.initials: M
authors.lastname: Costas
authors.forename: Xavi
authors.initials: X
authors.lastname: Ribas
authors.forename: Shannon S
authors.initials: SS
authors.lastname: Stahl
mesh_terms: D001555:Benzene Derivatives / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D006571:Heterocyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D007700:Kinetics; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D001555:Benzene Derivatives; D006571:Heterocyclic Compounds; D009942:Organometallic Compounds; D003300:Copper; D010100:Oxygen