A new divergent and efficient synthesis of substituted 2-aminoimidazoles 5 and 6 has been developed starting from the readily available 2-aminopyrimidines 1 and α-bromocarbonyl compounds 2, using conventional heating or microwave irradiation. Thus, the cleavage of 1, 2, 3-substituted imidazo [1, 2-a] pyrimidin-1-ium salts 4 with hydrazine or secondary amines led to 1, 4, 5-trisubstituted 2-aminoimidazoles 5, when the hydrazinolysis of 2-hydroxy-2, 3 ...