A series of asymmetrical substituted tetrahydropyrimidinium salts and different kinds of bridged bis-tetrahydropyrimidinium salts were prepared through the quaterization of tetrahydropyrimidine or the dehydrogenation of hexahydropyrimidine. They were characterized and used as NHC precursors in the palladium catalyzed Buchwald-Hartwig amination reaction. The in situ formed catalytic system Pd(OAc)(2)/tetrahydropyrimidinium and (BuOK)-Bu-t catalyzed the amination of heteroaryl halides and heterocyclic amines effectively, producing the heterocyclic amine functionalized heteroaryl derivatives in high yields.