Iron-Catalyzed Enantioselective Epoxidations with Various Oxidants: Evidence for Different Active Species and Epoxidation Mechanisms | Sciact - CRIS-система Института катализа

Iron-Catalyzed Enantioselective Epoxidations with Various Oxidants: Evidence for Different Active Species and Epoxidation Mechanisms Научная публикация

Журнал

ACS Catalysis
ISSN: 2155-5435

Вых. Данные

Год: 2017, Том: 7, Номер: 1, Страницы: 60-69 Страниц : 10 DOI: 10.1021/acscatal.6b02851

Ключевые слова

asymmetric epoxidation, bioinspired catalysis, enantioselectivity, EPR, iron, mechanism

Авторы

Zima Alexandra M. ^1,2 , Lyakin Oleg Y. ^1,2 , Ottenbacher Roman V. ^1,2 , Bryliakov Konstantin P. ^1,2 , Talsi Evgenii 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 (2)

1	Федеральное агентство научных организаций России	V.44.2.4.
2	Российский фонд фундаментальных исследований	16-29-10666

Iron complexes with chiral bipyrrolidine-derived aminopyridine (PDP) ligands are among the most efficient Fe-based bioinspired catalysts for regio- and stereoselective oxidation of C–H and C═C moieties with hydrogen peroxide. Besides hydrogen peroxide, other oxidants (peroxycarboxylic acids and organic hydroperoxides) can be effectively used. In this work, we have examined the mechanistic landscape of the Fe(PDP) catalyst family with various oxidants: H2O2, organic hydroperoxides, and peracids. The combined EPR spectroscopic, enantioselectivity, Hammett, Z-stilbene epoxidation stereoselectivity, and 18O-labeling data witness that the same oxoiron complexes [(L)FeV═O(OC(O)R)]2+ are the actual epoxidizing species in both the catalyst systems (L)Fe/H2O2/carboxylic acid and (L)Fe/AlkylOOH/carboxylic acid. On the contrary, in the systems (L)Fe/R2C(O)OOH (R2 = CH3 or 3–Cl-C6H4), in the presence or in the absence of carboxylic acid, the epoxidation is predominantly conducted by the acylperoxo-iron(III) intermediates [(L)FeIII(OOC(O)R2)]2+, in a concerted fashion.

Zima A.M. , Lyakin O.Y. , Ottenbacher R.V. , Bryliakov K.P. , Talsi E.P.
Iron-Catalyzed Enantioselective Epoxidations with Various Oxidants: Evidence for Different Active Species and Epoxidation Mechanisms

ACS Catalysis. 2017. V.7. N1. P.60-69. DOI: 10.1021/acscatal.6b02851 WOS Scopus РИНЦ CAPlusCA OpenAlex

Полный текст от издателя

Поступила в редакцию:	6 окт. 2016 г.
Принята к публикации:	3 нояб. 2016 г.
Опубликована online:	3 дек. 2016 г.
Опубликована в печати:	6 янв. 2017 г.

Web of science:	WOS:000391783200006
Scopus:	2-s2.0-85019668398
РИНЦ:	32051750
Chemical Abstracts:	2016:1821853
Chemical Abstracts (print):	166:65135
OpenAlex:	W2551091103

БД	Цитирований
Web of science	54
Scopus	57
РИНЦ	46
OpenAlex	64