Mechanism of the oxidation of o-nitro- and o-benzoylbenzeneselenenic acids by peracids, hydroperoxides, and hydrogen peroxide

Kice, John L.; Chiou, Shishue; Weclas, Ludmilla

doi:10.1021/jo00214a020

Cited by 7 publications

(1 citation statement)

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“…The oxidation path of diselenides by H2O2 or generally by peroxides was first proposed by Kice and Chiou [12], who described the formation of selenoxide and reduced species such water or alcohol molecules. As example, we can consider diphenyl diselenide (1), which is the most used catalyst in organic synthesis, but has also been thoroughly studied as antioxidant drug [13].…”

Section: H2o2 Reduction By Organoselenidesmentioning

confidence: 99%

Selenium-Catalyzed Reduction of Hydroperoxides in Chemistry and Biology

Orian

Flohé

2021

Antioxidants

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Among the chalcogens, selenium is the key element for catalyzed H2O2 reduction. In organic synthesis, catalytic amounts of organo mono- and di-selenides are largely used in different classes of oxidations, in which H2O2 alone is poorly efficient. Biological hydroperoxide metabolism is dominated by peroxidases and thioredoxin reductases, which balance hydroperoxide challenge and contribute to redox regulation. When their selenocysteine is replaced by cysteine, the cellular antioxidant defense system is impaired. Finally, classes of organoselenides have been synthesized with the aim of mimicking the biological strategy of glutathione peroxidases, but their therapeutic application has so far been limited. Moreover, their therapeutic use may be doubted, because H2O2 is not only toxic but also serves as an important messenger. Therefore, over-optimization of H2O2 reduction may lead to unexpected disturbances of metabolic regulation. Common to all these systems is the nucleophilic attack of selenium to one oxygen of the peroxide bond promoting its disruption. In this contribution, we revisit selected examples from chemistry and biology, and, by using results from accurate quantum mechanical modelling, we provide an accurate unified picture of selenium’s capacity of reducing hydroperoxides. There is clear evidence that the selenoenzymes remain superior in terms of catalytic efficiency.

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Section: H2o2 Reduction By Organoselenidesmentioning

confidence: 99%