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Reactivity Patterns of (Protonated) CompoundII and CompoundI of Cytochrome P450: Which is the Better Oxidant?

Title
Reactivity Patterns of (Protonated) CompoundII and CompoundI of Cytochrome P450: Which is the Better Oxidant?
Authors
Li, Xiao-XiPostils, VeronicaSun, WeiFaponle, Abayomi S.Sola, MiquelWang, YongNam, Wonwoode Visser, Sam P.
Ewha Authors
남원우
SCOPUS Author ID
남원우scopus
Issue Date
2017
Journal Title
CHEMISTRY-A EUROPEAN JOURNAL
ISSN
0947-6539JCR Link1521-3765JCR Link
Citation
vol. 23, no. 26, pp. 6406 - 6418
Keywords
cytochrome P450density functional calculationselectronic structurehydroxylationoxidation
Publisher
WILEY-V C H VERLAG GMBH
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
The cytochromes P450 are versatile enzymes in human physiology that perform substrate hydroxylation reactions extremely efficiently. In this work, we present results of a computational study on the reactivity patterns of Compound I, Compound II, and protonated Compound II with model substrates, and we address the question of which of these compounds is the most effective oxidant? All calculations, regardless of the substrate, implicated that Compound I is the superior oxidant of the three. However, Compound II and protonated Compound II were found to react with free energies of activation that are only a few kcalmol(-1) higher in energy than those obtained with Compound I. Therefore, Compound II and protonated Compound II should be able to react with aliphatic groups with moderate C-H bond strengths. We have analysed all results in detail and have given electronic, thermochemical, valence bond, and molecular orbital rationalizations on the reactivity differences and explained experimental product distributions. Overall, the findings implied that alternative oxidants could operate alongside Compound I in complex reaction mechanisms of enzymatic and synthetic iron porphyrinoid complexes.
DOI
10.1002/chem.201700363
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자연과학대학 > 화학·나노과학전공 > Journal papers
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