title: Copper-catalyzed oxaziridine-mediated oxidation of C-H bonds.
abstract: The highly regio- and chemoselective oxidation of activated C-H bonds has been observed via copper-catalyzed reactions of oxaziridines. The oxidation proceeded with a variety of substrates, primarily comprising allylic and benzylic examples, as well as one example of an otherwise unactivated tertiary C-H bond. The mechanism of the reaction is proposed to involve single-electron transfer to the oxaziridines to generate a copper-bound radical anion, followed by hydrogen atom abstraction and collapse to products, with regeneration of the catalyst by a final single-electron transfer event. The involvement of allylic radical intermediates was supported by a radical-trapping experiment with TEMPO.
authors: Department of Medicinal Chemistry, University of Kansas, Del Shankel Structural Biology Center, 2121 Simons Drive, West Campus, Lawrence, Kansas 66047, United States.
authors: Hashim F
authors: HF
authors: Motiwala
authors: Belgin
authors: B
authors: Gülgeze
authors: Jeffrey
authors: J
authors: Aubé
mesh_terms: D001388:Aziridines / Q000737:chemistry*; D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D003497:Cyclic N-Oxides; D004579:Electron Transport; D004583:Electrons; D006859:Hydrogen / Q000737:chemistry*; D007700:Kinetics; D009682:Magnetic Resonance Spectroscopy; D010084:Oxidation-Reduction; D019097:Spin Trapping; D013237:Stereoisomerism
chemical_list: D001388:Aziridines; D003497:Cyclic N-Oxides; D002244:Carbon; D003300:Copper; D006859:Hydrogen; C003959:TEMPO