Palladium-Aminopyridine Catalyzed C−H Oxygenation: Probing the Nature of Metal Based Oxidant | Sciact - CRIS-система Института катализа

Palladium-Aminopyridine Catalyzed C−H Oxygenation: Probing the Nature of Metal Based Oxidant Научная публикация

Журнал

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

Вых. Данные

Год: 2021, Том: 13, Номер: 24, Страницы: 5109-5120 Страниц : 12 DOI: 10.1002/cctc.202101345

Ключевые слова

C−H activation; intermediate; mechanism; oxyl; palladium; peracetic acid; selective oxidation

Авторы

Lubov Dmitry P. ¹ , Bryliakova Anna A. ^2,3 , Samsonenko Denis G. ⁴ , Sheven Dmitriy G. ⁴ , Talsi Evgenii P. ¹ , Bryliakov Konstantin P. ¹

Организации

1	Boreskov Institute of Catalysis, Lavrentieva 5, Novosibirsk 630090 (Russia)
2	Novosibirsk State University, Pirogova 1, Novosibirsk 630090 (Russia)
3	Novosibirsk R&D Center, Inzhenernaya 20, Novosibirsk 630090 (Russia)
4	Nikolaev Institute of Inorganic Chemistry, Pr. Lavrentieva 3, Novosibirsk 630090 (Russia)

Информация о финансировании (3)

1	Российский научный фонд	17-13-01117
2	Министерство науки и высшего образования Российской Федерации (с 15 мая 2018)	FWUZ-2021-0005 (121031700313-8)
3	Министерство науки и высшего образования Российской Федерации (с 15 мая 2018)	FWUZ-2021-0001 (121031700321-3)

A mechanistic study of direct selective oxidation of benzylic C(sp3)−H groups with peracetic acid, catalyzed by palladium complexes with tripodal amino-tris(pyriylmethyl) ligands, is presented. The oxidation of arylalkanes having secondary and tertiary benzylic C−H groups, predominantly yields, depending on the substrate and conditions, either the corresponding ketones or alcohols. One of the three 2-pyriylmethyl moieties, which is pending in the starting catalyst, apparently, facilitates the active species formation and takes part in stabilization of the high-valent Pd center in the active species, occupying the axial coordination site of palladium. The catalytic, as well as isotopic labeling experiments, in combination with ESI-MS data and DFT calculations, point out palladium oxyl species as possible catalytically active sites, operating essentially via C−H abstraction/oxygen rebound pathway. For the ketones formation, O−H abstraction/в-scission mechanism has been proposed. © 2021 Wiley-VCH GmbH

Lubov D.P. , Bryliakova A.A. , Samsonenko D.G. , Sheven D.G. , Talsi E.P. , Bryliakov K.P.
Palladium-Aminopyridine Catalyzed C−H Oxygenation: Probing the Nature of Metal Based Oxidant
ChemCatChem. 2021. V.13. N24. P.5109-5120. DOI: 10.1002/cctc.202101345 WOS Scopus РИНЦ CAPlus OpenAlex

Поступила в редакцию:	8 сент. 2021 г.
Принята к публикации:	21 сент. 2021 г.
Опубликована online:	30 сент. 2021 г.
Опубликована в печати:	15 дек. 2021 г.

Web of science:	WOS:000714551600001
Scopus:	2-s2.0-85118583343
РИНЦ:	47522964
Chemical Abstracts:	2021:2432452
OpenAlex:	W3203361724

БД	Цитирований
Scopus	7
Web of science	7
РИНЦ	6
OpenAlex	7