Nickel-catalysed sequential amination of aryl- and heteroaryl di- and trichlorides

Unsymmetrical 1,3-diaminobenzenes and diaminopyridines were efficiently prepared by reaction of 3-chloroanilines and chloroaminopyridines with amines via a nickel-catalysed amination. The Ni/2,2′-bipyridine catalyst is also effective for the sequential amination of aryl trichlorides. After a first selective monoamination of 1,3,5-trichlorobenzene, the obtained 3,5-dichloroanilines were subsequently transformed into novel and unsymmetrical 1,3,5-triaminobenzenes.