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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

Реферат: 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.
Библиографическая ссылка: 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
Файлы: Полный текст от издателя
Даты:
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.
Идентификаторы БД:
Web of science: WOS:000391783200006
Scopus: 2-s2.0-85019668398
РИНЦ: 32051750
Chemical Abstracts: 2016:1821853
Chemical Abstracts (print): 166:65135
OpenAlex: W2551091103
Цитирование в БД:
БД Цитирований
Web of science 54
Scopus 57
РИНЦ 46
OpenAlex 64
Альметрики: