Concepedia

Which Oxidant Is Really Responsible for P450 Model Oxygenation Reactions? A Kinetic Approach

Alicja Franke, Christoph Fertinger, Rudi van Eldik

Angewandte Chemie International Edition · 2008 · 56 citations · 21 references

DOI

Concepts

Abstract

A rate-fate fête: Direct kinetic studies on epoxidation and sulfoxidation reactions revealed that the oxygenating capability of [(TMP+.)FeIVO] is orders of magnitude higher than that of [FeIII(TMP)(m-CPBA)]. Under catalytic turnover conditions, the relative ratio between the rate of OO bond heterolytic cleavage and the rate of oxygen transfer from the [FeIII(TMP)(m-CPBA)] intermediate to the substrate, should be taken into consideration. m-CPBA=m-chloroperbenzoic acid, TMP=meso-tetramesitylporphyrin.

References

21

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Searching for the Second Oxidant in the Catalytic Cycle of Cytochrome P450:  A Theoretical Investigation of the Iron(III)-Hydroperoxo Species and Its Epoxidation Pathways

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Epoxidation of olefins by cytochrome P450: Evidence from site-specific mutagenesis for hydroperoxo-iron as an electrophilic oxidant

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Reactivities of Mononuclear Non-Heme Iron Intermediates Including Evidence that Iron(III)−Hydroperoxo Species Is a Sluggish Oxidant

Mi Joo Park, Jimin Lee, Yumi Suh et al. · Journal of the American Chemical Society · 2006 · 240 citations

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Peroxo-iron and oxenoid-iron species as alternative oxygenating agents in cytochrome P450-catalyzed reactions: switching by threonine-302 to alanine mutagenesis of cytochrome P450 2B4.

A D Vaz, Steven J. Pernecky, Gregory M. Raner et al. · Proceedings of the National Academy of Sciences · 1996 · 196 citations · Full text

, , +16