Extremely Fast Hydrogen Atom Transfer between Nitroxides and HOO· Radicals and Implication for Catalytic Coantioxidant Systems

Journal of the American Chemical Society
Andrea BaschieriRiccardo Amorati

Abstract

We report a novel coantioxidant system based on TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl radical) that, in biologically relevant model systems, rapidly converts chain-carrying alkylperoxyl radicals to HOO·. Extremely efficient quenching of HOO· by TEMPO blocks the oxidative chain. Rate constants in chlorobenzene were measured to be 1.1 × 109 M-1 s-1 for the reductive reaction TEMPO + HOO· → TEMPOH + O2 and 5.0 × 107 M-1 s-1 for the oxidative reaction TEMPOH + HOO· → TEMPO + H2O2. These rate constants are significantly higher than that associated with the reaction of HOO· with α-tocopherol, Nature's best lipid soluble antioxidant ( k = 1.6 × 106 M-1 s-1). These data show that in the presence of ROO·-to-HOO· chain-transfer agents, which are common in lipophilic environments, the TEMPO/TEMPOH couple protects organic molecules from oxidation by establishing an efficient reductive catalytic cycle. This catalytic cycle provides a new understanding of the efficacy of the antioxidant capability of TEMPO in nonaqueous systems and its potential to act as a chemoprotective against radical damage.

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Citations

Apr 27, 2021·The Journal of Organic Chemistry·Ron ShahDerek A Pratt
May 27, 2021·Chemical Society Reviews·Julian Helberg, Derek A Pratt
Jun 23, 2021·ACS Applied Materials & Interfaces·Damiano GenoveseNelsi Zaccheroni
Jul 3, 2021·Journal of the American Chemical Society·Cheng YangCorey R J Stephenson
Sep 20, 2019·The Journal of Organic Chemistry·Andrea BaschieriLetizia Sambri
Jan 23, 2019·The Journal of Organic Chemistry·Massimo BiettiMichela Salamone
Dec 8, 2021·Journal of Materials Chemistry. B, Materials for Biology and Medicine·Fabio MollicaRiccardo Amorati

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