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Oxidizing intermediates in cytochrome P450 model reactions

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Abstract

Oxoiron(IV) porphyrin π-cation radicals have been considered as the sole reactive species in the catalytic oxidation of organic substrates by cytochromes P450 and their iron porphyrin models over the past two decades. Recent studies from several laboratories, however, have provided experimental evidence that multiple oxidizing species are involved in the oxygen transfer reactions and that the mechanism of oxygen transfer is much more complex than initially believed. In this Commentary, reactive intermediates that have been shown or proposed to be involved in iron porphyrin complex-catalyzed oxidation reactions are reviewed. Particularly, the current controversy on the oxoiron(IV) porphyrin π-cation radical as a sole reactive species versus the involvement of multiple oxidizing species in oxygen transfer reactions is discussed.

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Abbreviations

F 5 PhIO:

pentafluoroiodosylbenzene

m-CPBA:

m-chloroperbenzoic acid

OEP:

dianion of octaethylporphyrin

PhIO:

iodosylbenzene

PPAA:

peroxyphenylacetic acid

TDCPP:

dianion of meso-tetrakis(2,6-dichlorophenyl)porphyrin

TMP:

dianion of meso-tetramesitylporphyrin

TPFPP:

dianion of meso-tetrakis(pentafluorophenyl)porphyrin

TPP:

dianion of meso-tetraphenylporphyrin

TTPPP:

dianion of meso-tetrakis(2,4,6-triphenylphenyl)porphyrin

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Acknowledgements

This work was supported by the Ministry of Science and Technology of Korea through the Creative Research Initiative Program and the Korea Science and Engineering Foundation (R02-2003-000-10047-0).

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Authors and Affiliations

  1. Department of Chemistry, Division of Nano Sciences, and Center for Biomimetic Systems, Ewha Womans University, 120-750, Seoul , Korea

    Wonwoo Nam, Yon Ok Ryu & Woon Ju Song

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  1. Wonwoo Nam
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Correspondence to Wonwoo Nam.

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Nam, W., Ryu, Y.O. & Song, W.J. Oxidizing intermediates in cytochrome P450 model reactions. J Biol Inorg Chem 9, 654–660 (2004). https://doi.org/10.1007/s00775-004-0577-5

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