Abstract The reaction of heteroaryl chlorides in the pyrimidine, pyrazine and quinazoline series with amines in water in the presence of KF results in a facile SN Ar reaction and N- arylation. The reaction is less satisfactory with pyridines unless an additional electron- withdrawing group is present. The results showed that the transition-metal-free SN Ar reaction not only compares favourably to palladium-catalysed coupling reactions but also ...