Highly Enantioselective C−H Oxidation of Arylalkanes with H2O2 in the Presence of Chiral Mn-Aminopyridine Complexes | Sciact - CRIS-система Института катализа

Highly Enantioselective C−H Oxidation of Arylalkanes with H2O2 in the Presence of Chiral Mn-Aminopyridine Complexes Научная публикация

Журнал

ChemCatChem
ISSN: 1867-3880 , E-ISSN: 1867-3899

Вых. Данные

Год: 2017, Том: 9, Номер: 24, Страницы: 4580-4586 Страниц : 7 DOI: 10.1002/cctc.201701169

Ключевые слова

asymmetric catalysis, C−H hydroxylation, enzyme models, hydrogen peroxide, manganese

Авторы

Talsi Evgenii P. ^1,2 , Samsonenko Denis G. ^1,3 , Ottenbacher Roman V. ^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 (1)

Российский научный фонд

17-13-01117

Bioinspired chiral Mn-aminopyridine complexes [(S,S)-LMnII(OTf)2] and [(R,R)-LMnII(OTf)2] (where (S,S)-L=(2S,2′S)-1,1′-bis((3-methyl-4-(2,2,2-trifluoroethoxy)pyridin-2-yl)methyl)-2,2′-bipyrrolidine, and (R,R)-L=(2R,2′R)-1,1′-bis((3-methyl-4-(2,2,2-trifluoroethoxy)pyridin-2-yl)methyl)-2,2′-bipyrrolidine) have been shown to efficiently catalyze the benzylic C−H oxidation of arylalkanes with hydrogen peroxide in the presence of carboxylic acid additives, affording enantiomerically enriched 1-arylalkanols and the corresponding ketones. Optically pure additive N-Boc-(L)-proline, in combination with [(R,R)-LMnII(OTf)2] complex, affords 1-arylalkanols in up to 86 % ee, which is the highest reported enantioselectivity for direct benzylic hydroxylations with H2O2 in the presence of transition-metal catalysts. Oxidative kinetic resolution only slightly contributes to the increase of the observed enantiomeric excess over the reaction course. The observed kH/kD values (3.5–3.6 for the oxidation of ethylbenzene/d10-ethylbenzene) and competitive oxidation data are consistent with either a hydrogen-atom transfer/oxygen rebound or hydride transfer/oxygen rebound asymmetric hydroxylation mechanism.

Talsi E.P. , Samsonenko D.G. , Ottenbacher R.V. , Bryliakov K.P.
Highly Enantioselective C−H Oxidation of Arylalkanes with H2O2 in the Presence of Chiral Mn-Aminopyridine Complexes
ChemCatChem. 2017. V.9. N24. P.4580-4586. DOI: 10.1002/cctc.201701169 WOS Scopus РИНЦ CAPlusCA OpenAlex

Поступила в редакцию:	18 июл. 2017 г.
Опубликована online:	10 авг. 2017 г.
Опубликована в печати:	20 дек. 2017 г.

Web of science:	WOS:000418390700018
Scopus:	2-s2.0-85029396833
РИНЦ:	35479178
Chemical Abstracts:	2017:1869643
Chemical Abstracts (print):	168:46187
OpenAlex:	W2744584509

БД	Цитирований
Web of science	46
Scopus	46
РИНЦ	43
OpenAlex	48