Energetics for the oxygen rebound mechanism of alkane hydroxylation by the iron-oxo species of cytochrome P450

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Abstract

Density-functional-theory calculational results on the reaction pathway for alkane hydroxylation by a compound I model of cytochrome P450 are discussed. Our calculations demonstrate that the transition state for the H-atom abstraction of ethane involves a linear (Fe)O···H···C array and that the resultant carbon radical is bound to the iron-hydroxo species. This comptational result is partly consistent with the oxygen rebound mechanism in that the direct H-atom abstraction by the iron-oxo species takes place in the initial stages of the reaction pathway. However, the iron-hydroxo species cannot be viewed as a stable reaction intermediate in view of the energy diagram. Our results may not be consistent with the model of a free radical species with a finite lifetime and barrier to displacement of the OH group from the iron center that is commonly assumed and typically stated for the oxygen rebound mechanism.

Original languageEnglish
Pages (from-to)2669-2673
Number of pages5
JournalBulletin of the Chemical Society of Japan
Volume73
Issue number12
DOIs
Publication statusPublished - Dec 1 2000
Externally publishedYes

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Hydroxylation
Alkanes
Cytochrome P-450 Enzyme System
Iron
Oxygen
Reaction intermediates
Atoms
Ethane
Free Radicals
Density functional theory
Carbon

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

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title = "Energetics for the oxygen rebound mechanism of alkane hydroxylation by the iron-oxo species of cytochrome P450",
abstract = "Density-functional-theory calculational results on the reaction pathway for alkane hydroxylation by a compound I model of cytochrome P450 are discussed. Our calculations demonstrate that the transition state for the H-atom abstraction of ethane involves a linear (Fe)O···H···C array and that the resultant carbon radical is bound to the iron-hydroxo species. This comptational result is partly consistent with the oxygen rebound mechanism in that the direct H-atom abstraction by the iron-oxo species takes place in the initial stages of the reaction pathway. However, the iron-hydroxo species cannot be viewed as a stable reaction intermediate in view of the energy diagram. Our results may not be consistent with the model of a free radical species with a finite lifetime and barrier to displacement of the OH group from the iron center that is commonly assumed and typically stated for the oxygen rebound mechanism.",
author = "Kazunari Yoshizawa and Yoshihito Shiota and Y. Kagawa",
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T1 - Energetics for the oxygen rebound mechanism of alkane hydroxylation by the iron-oxo species of cytochrome P450

AU - Yoshizawa, Kazunari

AU - Shiota, Yoshihito

AU - Kagawa, Y.

PY - 2000/12/1

Y1 - 2000/12/1

N2 - Density-functional-theory calculational results on the reaction pathway for alkane hydroxylation by a compound I model of cytochrome P450 are discussed. Our calculations demonstrate that the transition state for the H-atom abstraction of ethane involves a linear (Fe)O···H···C array and that the resultant carbon radical is bound to the iron-hydroxo species. This comptational result is partly consistent with the oxygen rebound mechanism in that the direct H-atom abstraction by the iron-oxo species takes place in the initial stages of the reaction pathway. However, the iron-hydroxo species cannot be viewed as a stable reaction intermediate in view of the energy diagram. Our results may not be consistent with the model of a free radical species with a finite lifetime and barrier to displacement of the OH group from the iron center that is commonly assumed and typically stated for the oxygen rebound mechanism.

AB - Density-functional-theory calculational results on the reaction pathway for alkane hydroxylation by a compound I model of cytochrome P450 are discussed. Our calculations demonstrate that the transition state for the H-atom abstraction of ethane involves a linear (Fe)O···H···C array and that the resultant carbon radical is bound to the iron-hydroxo species. This comptational result is partly consistent with the oxygen rebound mechanism in that the direct H-atom abstraction by the iron-oxo species takes place in the initial stages of the reaction pathway. However, the iron-hydroxo species cannot be viewed as a stable reaction intermediate in view of the energy diagram. Our results may not be consistent with the model of a free radical species with a finite lifetime and barrier to displacement of the OH group from the iron center that is commonly assumed and typically stated for the oxygen rebound mechanism.

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