Mechanism of Selective C–H Hydroxylation Mediated by Manganese Aminopyridine Enzyme Models Full article
| Journal |
ACS Catalysis
ISSN: 2155-5435 |
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| 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 |
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| Affiliations |
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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 OpenAlex ANCAN
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 OpenAlex ANCAN
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 |
| ≡ OpenAlex: | W2324686673 |
| ≡ Chemical Abstracts: | 2014:1888923 |
| ≡ Chemical Abstracts (print): | 162:62078 |