Direct observation of an oxepin from a bacterial cytochrome P450-catalyzed oxidation

Stok, Jeanette E., Chow, Sharon, Krenske, Elizabeth H., Farfan Soto, Clementina, Matyas, Csongor, Poirier, Raymond A., Williams, Craig M. and De Voss, James J. (2016) Direct observation of an oxepin from a bacterial cytochrome P450-catalyzed oxidation. Chemistry: A European Journal, 22 13: 4408-4412. doi:10.1002/chem.201600246

Author Stok, Jeanette E.
Chow, Sharon
Krenske, Elizabeth H.
Farfan Soto, Clementina
Matyas, Csongor
Poirier, Raymond A.
Williams, Craig M.
De Voss, James J.
Title Direct observation of an oxepin from a bacterial cytochrome P450-catalyzed oxidation
Journal name Chemistry: A European Journal   Check publisher's open access policy
ISSN 1521-3765
Publication date 2016-02-16
Sub-type Article (original research)
DOI 10.1002/chem.201600246
Open Access Status Not Open Access
Volume 22
Issue 13
Start page 4408
End page 4412
Total pages 6
Place of publication Weinheim, Germany
Publisher Wiley - V C H Verlag
Collection year 2017
Language eng
Formatted abstract
The cytochromes P450 are hemoproteins that catalyze a range of oxidative C−H functionalization reactions, including aliphatic and aromatic hydroxylation. These transformations are important in a range of biological contexts, including biosynthesis and xenobiotic biodegradation. Much work has been carried out on the mechanism of aliphatic hydroxylation, implicating hydrogen atom abstraction, but aromatic hydroxylation is postulated to proceed differently. One mechanism invokes as the key intermediate an arene oxide (and/or its oxepin tautomer). Conclusive isolation of this intermediate has remained elusive and, currently, direct formation of phenols from a Meisenheimer intermediate is believed to be favored. We report here the identification of a P450 [P450cam (CYP101A1) and P450cin (CYP176A1)]-generated arene oxide as a product of in vitro oxidation of tert-butylbenzene. Computations (CBS-QB3) predict that the arene oxide and oxepin have similar stabilities to other arene oxides/oxepins implicated (but not detected) in P450-mediated transformations, suggesting that arene oxides can be unstable terminal products of P450-catalyzed aromatic oxidation that can explain the origin of some observed metabolites.
Keyword Arene oxide
Benzene oxide
Cytochrome P450
Tert-butyl benzene
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: HERDC Pre-Audit
School of Chemistry and Molecular Biosciences
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Created: Fri, 19 Feb 2016, 10:24:20 EST by Mrs Louise Nimwegen on behalf of School of Chemistry & Molecular Biosciences