Palladium-Aminopyridine Catalyzed C−H Oxygenation: Probing the Nature of Metal Based Oxidant | Sciact - CRIS-system of Boreskov Institute of Catalysis

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

Journal

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

Output data

Year: 2021, Volume: 13, Number: 24, Pages: 5109-5120 Pages count : 12 DOI: 10.1002/cctc.202101345

Tags

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

Authors

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

Affiliations

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)

Funding (3)

1	Russian Science Foundation	17-13-01117
2	Ministry of Science and Higher Education of the Russian Federation	FWUZ-2021-0005 (121031700313-8)
3	Ministry of Science and Higher Education of the Russian Federation	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 AN OpenAlex

Submitted:	Sep 8, 2021
Accepted:	Sep 21, 2021
Published online:	Sep 30, 2021
Published print:	Dec 15, 2021

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

DB	Citing
Scopus	7
Web of science	7
Elibrary	7
OpenAlex	7