Abstract A mild and rapid procedure to the synthesis of 2-substituted pyrimidines was developed via sequential functionalization of easily available Biginelli 3, 4- dihydropyrimidine-2 (1H)-ones via oxidation, esterification, followed by cross-coupling reaction of pyrimidin-2-yl sulfonates with N, S, and O nucleophiles in PEG-400 as a green reaction medium at room temperature.