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A biomimetic study of cytochrome P450 related oxidations of toluenes using synthetic hemin

TitleA biomimetic study of cytochrome P450 related oxidations of toluenes using synthetic hemin
Publication TypeJournal Article
Year of Publication1996
AuthorsNakano, T, Agatsuma, N, Kodama, S, Kakuda, H, Dolphin, D
JournalBulletin of the Chemical Society of Japan
Volume69
Pagination3513-3521
Date PublishedDec
Type of ArticleArticle
ISBN Number0009-2673
KeywordsALIPHATIC, AROMATIC-COMPOUNDS, CRYSTAL-STRUCTURE, DEPENDENT MONO-OXYGENASES, HYDROGEN-PEROXIDE, HYDROXYLATION, INDUCED, IRON(III) PORPHYRINS, LIVER MICROSOMAL CYTOCHROME-P-450, METABOLISM, MODEL SYSTEMS, RAT-LIVER
Abstract

A mechanistic study of the oxidation of toluene and its derivatives in a model system designed to mimic cytochrome P450 (P450) using iron tetrakis(2,6-dichlorophenyl)porphyrin chloride (FeTPPC8Cl) and pentafluoroiodosylbenzene (PFIB:C(6)F(5)lO) in dichloromethane is reported. The oxidation products were the corresponding benzyl alcohols and aldehydes; no further oxidation products were observed. The relative reaction rates were obtained in competitive reactions including the use of deuterated analogues. In the present model system, Hammett plots and isotope effects indicated conclusively that the rate-determining step was a hydrogen atom abstraction to the oxoiron intermediate which was then followed by a rebound of an OH group. The concerted mechanism and the rebound mechanism were discussed in terms of the differences in reactivities between the model system and natural P450 enzymes and similar monooxygenation enzymes.

URL<Go to ISI>://A1996WB84400017