Highly Enantioselective Bioinspired Epoxidation of Electron-Deficient Olefins with H2O2 on Aminopyridine Mn Catalysts | Sciact - CRIS-система Института катализа

Highly Enantioselective Bioinspired Epoxidation of Electron-Deficient Olefins with H2O2 on Aminopyridine Mn Catalysts Научная публикация

Журнал

ACS Catalysis
ISSN: 2155-5435

Вых. Данные

Год: 2014, Том: 4, Номер: 5, Страницы: 1599-1606 Страниц : 8 DOI: 10.1021/cs500333c

Ключевые слова

asymmetric catalysis, enantioselective, epoxidation, hydrogen peroxide, intermediate, manganese, mechanism

Авторы

Ottenbacher Roman V. ^1,2 , Samsonenko Denis G. ^1,3 , 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
3	Nikolaev Institute of Inorganic Chemistry, Pr. Lavrentieva 3, Novosibirsk 630090, Russian Federation

Информация о финансировании (3)

1	Российский фонд фундаментальных исследований	12-03-00782
2	Российский фонд фундаментальных исследований	14-03-00102
3	Министерство образования и науки Российской Федерации

The asymmetric epoxidation of various electron-deficient olefins with H2O2 in the presence of a novel family of chiral bioinspired bipyrrolidine-derived aminopyridine manganese(II) complexes [LMII(OTf)2] is reported. High enantioselectivities (up to 99% ee) and epoxide selectivities (up to 100%), unprecedented for catalysts of this type, have been achieved; the catalysts perform up to 8500 catalytic turnovers. The presence of electron donors in the catalyst structure substantially enhances the enantioselectivity. Isotopic (18O) labeling studies provide evidence of the formation of the oxomanganese(V) active species. Hammett analysis suggests that the enantioselective epoxidation is rate-limited by the transfer of an electron to the MnVO intermediate, to form a short-lived acyclic (carbocationic) intermediate. In effect, the epoxide stereoconfiguration may be affected by the competition between the rotation around the Cα–Cβ single bond and the epoxide ring collapse.

Ottenbacher R.V. , Samsonenko D.G. , Talsi E.P. , Bryliakov K.P.
Highly Enantioselective Bioinspired Epoxidation of Electron-Deficient Olefins with H2O2 on Aminopyridine Mn Catalysts
ACS Catalysis. 2014. V.4. N5. P.1599-1606. DOI: 10.1021/cs500333c WOS Scopus РИНЦ CAPlusCA OpenAlex

Поступила в редакцию:	14 мар. 2014 г.
Принята к публикации:	10 апр. 2014 г.
Опубликована online:	22 апр. 2014 г.
Опубликована в печати:	2 мая 2014 г.

Web of science:	WOS:000335491200043
Scopus:	2-s2.0-84899821969
РИНЦ:	21876620
Chemical Abstracts:	2014:603411
Chemical Abstracts (print):	160:636322
OpenAlex:	W1972555729

БД	Цитирований
Web of science	112
Scopus	117
РИНЦ	114
OpenAlex	119