Triazole-assisted ruthenium-catalyzed C-H arylation of aromatic amides

Abstract

Site-selective ruthenium(II)-catalyzed direct arylation of amides was achieved through CH cleavages with modular auxiliaries, derived from easily accessible 1,2,3-triazoles. The triazolyldimethylmethyl (TAM) bidentate directing group was prepared in a highly modular fashion through copper(I)-catalyzed 1,3-dipolar cycloaddition and allowed for ruthenium-catalyzed CH arylations on arenes and heteroarenes, as well as alkenes, by using easy-to-handle aryl bromides as the arylating reagents. The triazole-assisted CH activation strategy was found to be widely applicable, to occur under mild reaction conditions, and the catalytic system was tolerant of important electrophilic functionalities. Notably, the flexible triazole-based auxiliary proved to be a more potent directing group for the optimized ruthenium(II)-catalyzed direct arylations, compared with pyridyl-substituted amides or substrates derived from 8-aminoquinoline.

Keywords: CH activation; amides; aryl halides; catalysis; ruthenium; triazoles.