Mechanism of Selective C–H Hydroxylation Mediated by Manganese Aminopyridine Enzyme Models | Sciact - CRIS-система Института катализа

Mechanism of Selective C–H Hydroxylation Mediated by Manganese Aminopyridine Enzyme Models Научная публикация

Журнал

ACS Catalysis
ISSN: 2155-5435

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

Ottenbacher Roman V. ^1,2 , Talsi Evgenii P. ^1,2 , Bryliakov Konstantin P. ^1,2

Организации

1	Novosibirsk State University, Pirogova 2, Novosibirsk 630090, Russian Federation
2	Boreskov Institute of Catalysis, Pr. Lavrentieva 5, Novosibirsk 630090, Russian Federation

Информация о финансировании (1)

Российский научный фонд

14-13-00158

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.

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 CAPlusCA OpenAlex

Поступила в редакцию:	3 сент. 2014 г.
Опубликована online:	24 нояб. 2014 г.
Опубликована в печати:	2 янв. 2015 г.

Web of science:	WOS:000347513400007
Scopus:	2-s2.0-84927753975
РИНЦ:	24976315
Chemical Abstracts:	2014:1888923
Chemical Abstracts (print):	162:62078
OpenAlex:	W2324686673

БД	Цитирований
Web of science	73
Scopus	78
РИНЦ	76
OpenAlex	84