Palladium‐Aminopyridine Catalyzed C−H Oxygenation: Probing the Nature of Metal Based Oxidant Научная публикация
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Chemcatchem
ISSN: 1867-3899 , E-ISSN: 1867-3880 |
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| Вых. Данные | Год: 2021, Том: 13, Номер: 24, Страницы: 5109-5120 Страниц : 12 DOI: 10.1002/cctc.202101345 | ||||||||
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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
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 |