Heteroarylation of Azine N-Oxides

Azine N-oxides undergo highly regioselective metalation with TMPZnCl center dot LiCl under mild conditions. A palladium-catalyzed Negishi cross-coupling reaction of the resulting organozinc species with heteroaromatic bromides provides heterobiaryls specifically oxidized at one nitrogen position in up to 95% yield.