Work

Catalytic C-Demethylation of Phenols and Anilines Enabled by a Removable Mono-Directing Group

Year: 2026

Type: article

Abstract: The activation of unstrained nonpolar C-C bonds, such as C(aryl)-C(alkyl) bonds, remains challenging to achieve. Existing catalytic strategies predominantly rely on bidentate chelating directing groups (DGs) or special substrates. Herein, we report a Ru-catalyzed activation of C(aryl)-C(methyl) bonds enabled by a removable mono-DG. By employing a bulky phosphinite or aminophosphine-DG that can be easily installed and removed later, a methyl group at the ortho position of phenols and anilines can be smoothly deleted under the hydrogenolysis condition. This reaction exhibits a broad substrate scope and excellent functional group tolerance. Mechanistic studies suggest that a Ru-hydride species generated in situ is responsible for the C(aryl)-C(methyl) bond activation, with methane identified as a byproduct.

Source: Journal of the American Chemical Society

DOI: 10.1021/jacs.6c01406

Authors: Yibin Xue, Liyan Kan, Linda Yiu, Congjun Yu, Guangbin Dong

Institution: University of Chicago

Language: English

Topic: Catalytic C–H Functionalization Methods

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funders: University of Chicago, National Institute of General Medical Sciences

Award: Catalytic C−C Activation/Functionalization of Ketones and Amides