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

Журнал Chemcatchem
ISSN: 1867-3899 , E-ISSN: 1867-3880
Вых. Данные Год: 2021, Том: 13, Номер: 24, Страницы: 5109-5120 Страниц : 12 DOI: 10.1002/cctc.202101345
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

Реферат: 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.
Библиографическая ссылка: 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 OpenAlex
Даты:
Поступила в редакцию: 8 сент. 2021 г.
Принята к публикации: 30 сент. 2021 г.
Опубликована online: 30 сент. 2021 г.
Опубликована в печати: 5 нояб. 2021 г.
Идентификаторы БД:
Web of science: WOS:000714551600001
Scopus: 2-s2.0-85118583343
OpenAlex: W3203361724
Цитирование в БД:
БД Цитирований
OpenAlex 7
Scopus 6
Web of science 7
Альметрики: