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

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

Journal

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

Output data

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

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

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.

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

Submitted:	Sep 8, 2021
Accepted:	Sep 30, 2021
Published online:	Sep 30, 2021
Published print:	Nov 5, 2021

Web of science:	WOS:000714551600001
Scopus:	2-s2.0-85118583343
OpenAlex:	W3203361724

DB	Citing
OpenAlex	6
Scopus	6
Web of science	6