Mechanism of Selective C–H Hydroxylation Mediated by Manganese Aminopyridine Enzyme Models Научная публикация
| Журнал |
ACS Catalysis
ISSN: 2155-5435 |
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| Вых. Данные | Год: 2015, Том: 5, Номер: 1, Страницы: 39-44 Страниц : 6 DOI: 10.1021/cs5013206 | ||||
| Ключевые слова | biomimetic catalysis, C-H hydroxylation, enzyme models, hydrogen peroxide, manganese, mechanism | ||||
| Авторы |
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| Организации |
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Информация о финансировании (1)
| 1 | Российский научный фонд | 14-13-00158 |
Реферат:
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.
Библиографическая ссылка:
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 CAPlusCA
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 CAPlusCA
Даты:
| Поступила в редакцию: | 3 сент. 2014 г. |
| Опубликована online: | 24 нояб. 2014 г. |
| Опубликована в печати: | 2 янв. 2015 г. |
Идентификаторы БД:
| ≡ Web of science: | WOS:000347513400007 |
| ≡ Scopus: | 2-s2.0-84927753975 |
| ≡ РИНЦ: | 24976315 |
| ≡ OpenAlex: | W2324686673 |
| ≡ Chemical Abstracts: | 2014:1888923 |
| ≡ Chemical Abstracts (print): | 162:62078 |