Palladium catalyzed selective benzylic C‒H alkoxylation

Palladium catalyzed selective benzylic C‒H alkoxylation Full article

Journal

Journal of Catalysis
ISSN: 0021-9517 , E-ISSN: 1090-2694

Output data

Year: 2026, Article number : 116895, Pages count : DOI: 10.1016/j.jcat.2026.116895

Authors

Lubov Dmitry P. ¹ , Ivanov Konstantin S. ² , Nefedov Andrey A. ^2,3 , Bryliakov Konstantin P. ¹

Affiliations

1	Zelinsky Institute of Organic Chemistry RAS, Leninsky Pr. 47, Moscow 119991, Russia
2	Novosibirsk State University, Pirogova 1, Novosibirsk 630090, Russia
3	Vorozhtsov Novosibirsk Institute of Organic Chemistry, Pr. Lavrentieva 9, Novosibirsk 630090, Russia

Palladium(II) complexes of the TPA family (TPA − tris(2-pyridylmethyl)amine) are known as highly regioselective catalysts of hydroxylation of 3° C(sp3)‒H groups with peroxycarboxylic acids. Recently, they have been shown to mediate the selective trifluoroethoxylation of organic substrates at benzylic Csingle bondH groups in the medium of 2,2,2-trifluoroethanol, giving the corresponding trifluoroethyl ethers in up to 73 % isolated yield. Herewith, we have developed the general approach to palladium catalyzed direct benzylic C(sp3)‒H alkoxylations, converting the substrates to the corresponding alkyl ethers in up to 95 % yield. The utility of the developed synthetic protocol is exemplified by the selective alkoxylation of several complex molecules of natural origin (steroids and terpenoids). Preliminary experimental data on the alkoxylation mechanism are discussed.

Lubov D.P. , Ivanov K.S. , Nefedov A.A. , Bryliakov K.P.
Palladium catalyzed selective benzylic C‒H alkoxylation
Journal of Catalysis. 2026. 116895 . DOI: 10.1016/j.jcat.2026.116895 OpenAlex

Submitted:	Feb 2, 2026
Published print:	Apr 22, 2026

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