[reaction: see text]. A highly regioselective amination of 6-aryl-2,4-dichloropyrimidine with aliphatic secondary amines and aromatic amines has been developed which strongly favors the formation of the C4-substituted product. The reactions with aliphatic amines are carried out using LiHMDS as the base and are catalyzed by Pd, while the aromatic amines require no catalyst.