Palladium catalyzed selective benzylic C ‒ H alkoxylation

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Palladium catalyzed selective benzylic C ‒ H alkoxylation. / Lubov, Dmitry P; Ivanov, Konstantin S ; Nefedov, Andrey A et al.

In: Journal of Catalysis, Vol. 459, 116895, 07.2026.

Research output: Contribution to journal › Article › peer-review

BibTeX

@article{8103adb0e4234e138c96a46e814c8f35,

title = "Palladium catalyzed selective benzylic C ‒ H alkoxylation",

abstract = "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 C−H 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.",

keywords = "Alkoxyation, C–H activation, Benzylic oxidation, Late",

author = "Lubov, {Dmitry P} and Ivanov, {Konstantin S} and Nefedov, {Andrey A} and Bryliakov, {Konstantin P}",

note = "The authors thank the Russian Science Foundation for the financial support of this work (synthetic and catalytic studies), grant 25-13-00108. AAN is grateful to the Ministry of Science and Higher Education, project for Vorozhtsov Novosibirsk Institute of Organic Chemistry (HR-MS measurements). The authors thank the Center for collective use of the Zelinsky Institute of Organic Chemistry RAS for the assistance with the NMR spectroscopic measurements.",

year = "2026",

month = jul,

doi = "10.1016/j.jcat.2026.116895",

language = "English",

volume = "459",

journal = "Journal of Catalysis",

issn = "0021-9517",

publisher = "Elsevier Science Publishing Company, Inc.",

}

RIS

TY - JOUR

T1 - Palladium catalyzed selective benzylic C ‒ H alkoxylation

AU - Lubov, Dmitry P

AU - Ivanov, Konstantin S

AU - Nefedov, Andrey A

AU - Bryliakov, Konstantin P

N1 - The authors thank the Russian Science Foundation for the financial support of this work (synthetic and catalytic studies), grant 25-13-00108. AAN is grateful to the Ministry of Science and Higher Education, project for Vorozhtsov Novosibirsk Institute of Organic Chemistry (HR-MS measurements). The authors thank the Center for collective use of the Zelinsky Institute of Organic Chemistry RAS for the assistance with the NMR spectroscopic measurements.

PY - 2026/7

Y1 - 2026/7

N2 - 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 C−H 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.

AB - 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 C−H 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.

KW - Alkoxyation

KW - C–H activation

KW - Benzylic oxidation

KW - Late

UR - https://www.scopus.com/pages/publications/105037149352

UR - https://www.mendeley.com/catalogue/82588804-5f8a-312c-809c-176db25a6910/

U2 - 10.1016/j.jcat.2026.116895

DO - 10.1016/j.jcat.2026.116895

M3 - Article

VL - 459

JO - Journal of Catalysis

JF - Journal of Catalysis

SN - 0021-9517

M1 - 116895

ER -

ID: 80161903