Arylation of Adamantanamines: X. Palladium- and Copper-Catalyzed Heteroarylation of Adamantane-Containing Amines with Bromopyridines

Abstract

The catalytic efficiencies of palladium(0) and copper(I) complexes in the amination of 2-bromopyridine and its fluorine-containing derivatives with (1-adamantyl)methanamine and 2-(1-adamantyloxy)ethanamine were compared. Both types of catalytic systems were shown to be applicable for the preparation of the corresponding N-pyridyl derivatives from 3- and 5-fluoro- and 4-, 5-, and 6-trifluoromethyl-2-bromopyridines. DavePhos was found to be the most efficient ligand in the Pd(0)-catalyzed reactions; however, the reactions with 2-bromo-4-(trifluoromethyl)pyridine and 2-bromo-5-(trifluoromethyl)pyridine were accompanied by formation of a considerable amount of the diarylation product. The diarylation process was significantly suppressed in the presence of copper(I) complexes.