A Predictably Selective Palladium-Catalyzed Aliphatic C-H Oxygenation

Dmitry P Lubov; Mikhail V Shashkov; Andrey A Nefedov; Konstantin P Bryliakov

doi:10.1021/acs.orglett.2c04371

A Predictably Selective Palladium-Catalyzed Aliphatic C-H Oxygenation

Org Lett. 2023 Mar 10;25(9):1359-1363. doi: 10.1021/acs.orglett.2c04371. Epub 2023 Feb 24.

Authors

Dmitry P Lubov^{1

2}, Mikhail V Shashkov¹, Andrey A Nefedov^{2

3}, Konstantin P Bryliakov^{1

2}

Affiliations

¹ Boreskov Institute of Catalysis, Pr. Lavrentieva 5, Novosibirsk 630090, Russian Federation.
² Novosibirsk State University, Pirogova 1, Novosibirsk 630090, Russia.
³ Vorozhtsov Novosibirsk Institute of Organic Chemistry, Pr. Lavrentieva 9, Novosibirsk 630090, Russia.

PMID: 36825896
DOI: 10.1021/acs.orglett.2c04371

Abstract

Direct oxygenation of nonactivated aliphatic C(sp³)-H groups with peroxycarboxylic acids in the presence of palladium tris(pyridylmethyl)amine complex (0.6 mol %) is reported, providing the corresponding hydroxylated derivatives in up to 94% yields. The oxidation of 3° C-H groups occurs stereospecifically, with the catalyst system demonstrating extremely high sensitivity to electronic effects (adamantane oxidation: 3°:2° up to >300). This suggests potential applications for the 3°-regioselective oxidative functionalization of complex molecules of natural origin.