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

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 OpenAlex CAPlusCA

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
≡ OpenAlex:	W2551091103
≡ Chemical Abstracts:	2016:1821853
≡ Chemical Abstracts (print):	166:65135

≡ Web of science	60	Сбор данных от 20.02.2026
≡ Scopus	60	Сбор данных от 15.02.2026
≡ РИНЦ	46	Сбор данных от 15.02.2026
≡ OpenAlex	70	Сбор данных от 15.02.2026