Abstract: | The carboxylate anion has been used as a directing group in the aromatic amination of electronically equivalent aryl bromides to afford selective ortho‐substituted derivatives (>99:1 selectivity; 60–80% yield) in the case of copper(I) catalysis. The solvent, base and equivalents of base were important factors in the success of this reaction. Complementary selectivity was achieved with palladium catalysis where the para‐substituted derivatives were produced selectively (>99% selectivity, 70–80% yield). |