Enantioselective Epoxidations of Olefins with Various Oxidants on Bioinspired Mn Complexes: Evidence for Different Mechanisms and Chiral Additive Amplification | Sciact - CRIS-система Института катализа

Enantioselective Epoxidations of Olefins with Various Oxidants on Bioinspired Mn Complexes: Evidence for Different Mechanisms and Chiral Additive Amplification Научная публикация

Журнал

ACS Catalysis
ISSN: 2155-5435

Вых. Данные

Год: 2016, Том: 6, Номер: 2, Страницы: 979-988 Страниц : 9 DOI: 10.1021/acscatal.5b02299

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 (2)

1	Федеральное агентство научных организаций России	V.44.2.4.
2	Российский фонд фундаментальных исследований	14-03-00102

It has been demonstrated that chiral manganese aminopyridine complexes [LMnII(OTf)2] are able to epoxidize olefins with excellent enantioselectivities (up to 99% ee, several examples) with various terminal oxidants (H2O2, alkyl hydroperoxides, peroxyacids, and iodosylarenes). The mechanisms of enantioselective olefin epoxidations on aminopyridine manganese(II) complexes [LMnII(OTf)2] with different oxidants are considered. The analysis of reaction products and epoxidation enantioselelctivity, Hammett correlations, and isotopic (18O) labeling studies bear evidence in favor of the formation of different oxidizing species in the presence of different terminal oxidants. The addition of cocatalytic additives (carboxylic acid or H2O) dramatically changes the catalytic behavior of catalyst systems Mn complex/hydrogen peroxide and Mn complex/alkyl hydroperoxide; in the presence of additives, the catalyst systems with H2O2 and alkyl hydroperoxides demonstrate very similar behaviors. Remarkably, in the presence of chiral additive Boc-protected (l)-proline, achiral Mn aminopyridine complexes catalyze the epoxidation of chalcone in an enantioselective fashion (with up to 60% ee), representing a rare example of chiral environment amplification.

Ottenbacher R.V. , Samsonenko D.G. , Talsi E.P. , Bryliakov K.P.
Enantioselective Epoxidations of Olefins with Various Oxidants on Bioinspired Mn Complexes: Evidence for Different Mechanisms and Chiral Additive Amplification
ACS Catalysis. 2016. V.6. N2. P.979-988. DOI: 10.1021/acscatal.5b02299 WOS Scopus РИНЦ CAPlusCA OpenAlex

Поступила в редакцию:	14 окт. 2015 г.
Принята к публикации:	24 дек. 2015 г.
Опубликована online:	12 янв. 2016 г.
Опубликована в печати:	5 февр. 2016 г.

Web of science:	WOS:000369774900059
Scopus:	2-s2.0-84957537042
РИНЦ:	26861051
Chemical Abstracts:	2015:2104411
Chemical Abstracts (print):	164:187629
OpenAlex:	W2236588896

БД	Цитирований
Web of science	60
Scopus	61
РИНЦ	63
OpenAlex	64