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Mechanism of Selective C–H Hydroxylation Mediated by Manganese Aminopyridine Enzyme Models Full article

Journal ACS Catalysis
ISSN: 2155-5435
Output data Year: 2015, Volume: 5, Number: 1, Pages: 39-44 Pages count : 6 DOI: 10.1021/cs5013206
Tags biomimetic catalysis, C-H hydroxylation, enzyme models, hydrogen peroxide, manganese, mechanism
Authors Ottenbacher Roman V. 1,2 , Talsi Evgenii P. 1,2 , Bryliakov Konstantin P. 1,2
Affiliations
1 Novosibirsk State University, Pirogova 2, Novosibirsk 630090, Russian Federation
2 Boreskov Institute of Catalysis, Pr. Lavrentieva 5, Novosibirsk 630090, Russian Federation

Funding (1)

1 Russian Science Foundation 14-13-00158

Abstract: The mechanism of selective oxidation of aliphatic C–H groups with H2O2 in the presence of aminopyridine Mn complexes, modeling the reactivities of natural oxygenases of the cytochrome P450 superfamily, has been examined. The oxygenation of C–H groups proceeds via hydrogen atom abstraction by the electrophilic metal site; the logarithm of C–H oxidation rates correlates linearly with bond dissociation energies for homolytic C–H bond cleavage. Hammett correlations and stereospecificity studies reflect the formation of a short-lived electron-deficient radical intermediate. Isotopic labeling studies confirm the incorporation of 18O from added H218O, thus providing so far lacking evidence for the oxomanganese(V)-mediated oxidation mechanism.
Cite: Ottenbacher R.V. , Talsi E.P. , Bryliakov K.P.
Mechanism of Selective C–H Hydroxylation Mediated by Manganese Aminopyridine Enzyme Models
ACS Catalysis. 2015. V.5. N1. P.39-44. DOI: 10.1021/cs5013206 WOS Scopus РИНЦ ANCAN OpenAlex
Dates:
Submitted: Sep 3, 2014
Published online: Nov 24, 2014
Published print: Jan 2, 2015
Identifiers:
Web of science: WOS:000347513400007
Scopus: 2-s2.0-84927753975
Elibrary: 24976315
Chemical Abstracts: 2014:1888923
Chemical Abstracts (print): 162:62078
OpenAlex: W2324686673
Citing:
DB Citing
Web of science 73
Scopus 78
Elibrary 76
OpenAlex 84
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