| Abstract: | Nuclear oxybromination of unprotected aromatic primary amines catalyzed by copper(II) acetate Cu(OAc)2] under mild conditions has been developed, in which bromide ions are used as halogenating agents and dioxygen as a final oxidant. The catalyst shows not only high regioselectivity for para‐ or ortho‐isomers but also a remarkable chemoselectivity for monobromination. Oxychlorination of aniline can also be performed under similar conditions, albeit with lower selectivities, with N‐phenylacetamide being the main by‐product. This simple catalytic method represents ecologically benign and economically attractive synthetic pathway to expensive low‐volume aromatic haloamines. |
