Copper-Catalyzed Monooxygenation of Phenols: Evidence for a Mononuclear Reaction Mechanism

The CuI salts [Cu(CH3 CN)4 ]PF and [Cu(oDFB)2 ]PF with the very weakly coordinating anion Al(OC(CF3 )3 )4- (PF) as well as [Cu(NEt3 )2 ]PF comprising the unique, linear bis-triethylamine complex [Cu(NEt3 )2 ]+ were synthesized and examined as catalysts for the conversion of monophenols to o-quinones. The activities of these CuI salts towards monooxygenation of 2,4-di-tert-butylphenol (DTBP-H) were compared to those of [Cu(CH3 CN)4 ]X salts with "classic" anions (BF4- , OTf- , PF6- ), revealing an anion effect on the activity of the catalyst and a ligand effect on the reaction rate. The reaction is drastically accelerated by employing CuII -semiquinone complexes as catalysts, indicating that formation of a CuII complex precedes the actual catalytic cycle. This result and other experimental observations show that with these systems the oxygenation of monophenols does not follow a dinuclear, but a mononuclear pathway analogous to that of topaquinone cofactor biosynthesis in amine oxidase.

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