Highly Enantioselective Undirected Catalytic Hydroxylation of Benzylic CH2 Groups with H2O2 | Sciact - CRIS-система Института катализа

Highly Enantioselective Undirected Catalytic Hydroxylation of Benzylic CH2 Groups with H2O2 Научная публикация

Журнал

Journal of Catalysis
ISSN: 0021-9517 , E-ISSN: 1090-2694

Вых. Данные

Год: 2020, Том: 390, Страницы: 170-177 Страниц : 8 DOI: 10.1016/j.jcat.2020.08.005

Ключевые слова

Asymmetric catalysis; C-H activation; Desaturation; Hydrogen peroxide; Manganese oxidation

Авторы

Ottenbacher Roman V. ^1,2 , Talsi Evgenii P. ^1,2 , Bryliakov Konstantin P. ^1,2

Организации

1	Novosibirsk State University, Pirogova 1, Novosibirsk 630090, Russia
2	Boreskov Institute of Catalysis, Pr. Lavrentieva 5, Novosibirsk 630090, Russia

Информация о финансировании (1)

Российский научный фонд

20-13-00032 (АААА-А20-120071590003-2)

Chiral bis-amine-bis-pyridine Mn complexes of the type [LMnII(OTf)2] (L is 2,2ʹ-bipyrrolidine derived chiral ligand, bearing trifluoroethoxy and methyl substituents), efficiently catalyze the enantioselective hydroxylation of organic substrates at benzylic CH2 positions with H2O2. The use of β-polyfluorinated alcohols instead of CH3CN as the reaction solvents enhances the yield of chiral secondary alcohol from 5–6% up to 50–70%. The enantiomeric purity of the alcohol can be further increased (up to 97% ee) by diluting the mixture with CH3CN at late stage, which facilitates stereoconvergent oxidative kinetic resolution of the alcohol formed. Using this one-pot sequential asymmetric hydroxylation/oxidative kinetic resolution approach, the oxidation of a series of 3,4-dihydrocoumarin derivatives and 3,4-dihydroquinolinone has been realized, affording the target 4-hydroxo compounds in 40–60% isolated yield and in up to 93% ee. Besides the 4-hydroxo derivatives, formation of 3,4-epoxidation and 3,4-desaturation byproducts has been observed in some cases, thus providing evidence for unprecedented substrate-dependent hydroxylase/desaturase/epoxidase reactivity of bis-amine-bis-pyridine Mn complexes.

Ottenbacher R.V. , Talsi E.P. , Bryliakov K.P.
Highly Enantioselective Undirected Catalytic Hydroxylation of Benzylic CH2 Groups with H2O2
Journal of Catalysis. 2020. V.390. P.170-177. DOI: 10.1016/j.jcat.2020.08.005 WOS Scopus РИНЦ CAPlusCA OpenAlex

Поступила в редакцию:	9 июл. 2020 г.
Принята к публикации:	3 авг. 2020 г.
Опубликована online:	12 авг. 2020 г.
Опубликована в печати:	1 окт. 2020 г.

Web of science:	WOS:000571126000002
Scopus:	2-s2.0-85089818642
РИНЦ:	45402859
Chemical Abstracts:	2020:1687084
Chemical Abstracts (print):	173:534501
OpenAlex:	W3048629394

БД	Цитирований
Scopus	43
Web of science	41
РИНЦ	37
OpenAlex	45