A base-promoted amination
of aromatic halides has been developed
using a limited amount of dimethylformamide (DMF) or amine as an amino
source. Various aryl halides, including F, Cl, Br, and I, have been
successfully aminated in good to excellent yields. Although the amination
of aromatic halides with amines or DMF is usually considered as an
aromatic nucleophilic substitution (SNAr) process, and
the reactivity of an aromatic halide is F > Cl > Br > I,
the reactivity
of aromatic halides in this system was found to be I > Br ≈
F > Cl. This protocol also showed a good regioselectivity for multihalogenated
aromatics. This protocol is valuable for industrial application due
to the simplicity of operation, the unrestricted availability of amino
sources and aromatic halides, transition metal-free conditions, no
requirement for solvent, and scalability.