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- W2213069300 abstract "Cooperative catalysis between CuII and redox-active organic cocatalysts is a key feature of important chemical and enzymatic aerobic oxidation reactions, such as alcohol oxidation mediated by Cu/TEMPO and galactose oxidase. Nearly 20 years ago, Markó and co-workers reported that azodicarboxylates, such as di-tert-butyl azodicarboxylate (DBAD), are effective redox-active cocatalysts in Cu-catalyzed aerobic alcohol oxidation reactions [Markó, I. E., et al. Science 1996, 274, 2044], but the nature of the cooperativity between Cu and azodicarboxylates is not well understood. Here, we report a mechanistic study of Cu/DBAD-catalyzed aerobic alcohol oxidation. In situ infrared spectroscopic studies reveal a burst of product formation prior to steady-state catalysis, and gas-uptake measurements show that no O2 is consumed during the burst. Kinetic studies reveal that the anaerobic burst and steady-state turnover have different rate laws. The steady-state rate does not depend on [O2] or [DBAD]. These results, together with other EPR and in situ IR spectroscopic and kinetic isotope effect studies, reveal that the steady-state mechanism consists of two interdependent catalytic cycles that operate in sequence: a fast CuII/DBAD pathway, in which DBAD serves as the oxidant, and a slow CuII-only pathway, in which CuII is the oxidant. This study provides significant insight into the redox cooperativity, or lack thereof, between Cu and redox-active organic cocatalysts in aerobic oxidation reactions." @default.
- W2213069300 created "2016-06-24" @default.
- W2213069300 creator A5036392431 @default.
- W2213069300 creator A5074617275 @default.
- W2213069300 date "2015-12-30" @default.
- W2213069300 modified "2023-09-27" @default.
- W2213069300 title "Mechanism of Copper/Azodicarboxylate-Catalyzed Aerobic Alcohol Oxidation: Evidence for Uncooperative Catalysis" @default.
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- W2213069300 doi "https://doi.org/10.1021/jacs.5b09940" @default.
- W2213069300 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/26694091" @default.
- W2213069300 hasPublicationYear "2015" @default.