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The FeIII(H2O2) complex as a highly efficient oxidant in sulfoxidation reactions: Revival of an underrated oxidant in cytochrome P450

Title
The FeIII(H2O2) complex as a highly efficient oxidant in sulfoxidation reactions: Revival of an underrated oxidant in cytochrome P450
Authors
Wang B.Li C.Cho K.-B.Nam W.Shaik S.
Ewha Authors
남원우
SCOPUS Author ID
남원우scopus
Issue Date
2013
Journal Title
Journal of Chemical Theory and Computation
ISSN
1549-9618JCR Link
Citation
vol. 9, no. 6, pp. 2519 - 2525
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
This work demonstrates that the FeIII(H2O 2) complex, which has been considered as an unlikely oxidant in P450, is actually very efficient in sulfoxidation reactions. Thus, Fe III(H2O2) undergoes a low-barrier nucleophilic attack by sulfur on the distal oxygen, resulting in heterolytic O-O cleavage coupled to proton transfer. We further show that FeIII(H 2O2) is an efficient sulfoxidation catalyst in synthetic iron porphyrin and iron corrolazine compounds. In all cases, Fe III(H2O2) performs the oxidation much faster than it converts to Cpd I and will therefore bypass Cpd I in the presence of a thioether. Thus, this paper not only suggests a plausible resolution of a longstanding issue in P450 chemistry regarding the "second oxidant" but also highlights a new mechanistic pathway for sulfoxidation reactions in P450s and their multitude of synthetic analogues. These findings have far-reaching implications for transition metal compounds, where H 2O2 is used as the terminal oxidant. © 2013 American Chemical Society.
DOI
10.1021/ct400190f
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자연과학대학 > 화학·나노과학전공 > Journal papers
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