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The alkenyl migration mechanism catalyzed by extradiol dioxygenases: a hybrid DFT study
Uppsala University, Disciplinary Domain of Medicine and Pharmacy, Faculty of Pharmacy, Department of Pharmaceutical Biosciences.
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2012 (English)In: Journal of Biological Inorganic Chemistry, ISSN 0949-8257, E-ISSN 1432-1327, Vol. 17, no 6, 881-890 p.Article in journal (Refereed) Published
Abstract [en]

6-Hydroxymethyl-6-methylcyclohexa-2,4-dienone is a mechanistic probe which when incubated with an extradiol dioxygenase yields a 2-tropolone product. This observation was originally interpreted as evidence supporting a direct heterolytic 1,2-alkenyl migration mechanism for a ring expansion reaction catalyzed by this class of Fe(II)-dependent nonheme enzymes (Xin and Bugg in J Am Chem Soc 130:10422-10430, 2008). In the work reported in this contribution we used quantum chemical methods to test whether such a mechanism is energetically possible and we found that it is not, neither for the mechanistic probe nor for the native catalytic cycle intermediate. Models of increasing complexity were used to calculate energy barriers to the heterolytic 1,2-alkenyl migration and alternative radical mechanisms. It was found that the former involves substantially higher barriers than the latter. A tentative radical mechanism that accounts for the transformation of the probe substrate to 2-tropolone was also proposed, and it involves acceptable barriers.

Place, publisher, year, edition, pages
2012. Vol. 17, no 6, 881-890 p.
Keyword [en]
Extradiol, Dioxygenase, Ring cleavage, O-O bond cleavage, Mechanistic probe
National Category
Medical and Health Sciences
Identifiers
URN: urn:nbn:se:uu:diva-179911DOI: 10.1007/s00775-012-0904-1ISI: 000306731100004OAI: oai:DiVA.org:uu-179911DiVA: diva2:547221
Available from: 2012-08-27 Created: 2012-08-27 Last updated: 2017-12-07Bibliographically approved

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Georgiev, Valentin

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