We have developed an easy method to construct diheteroaryls from α-aroylidineketene dithioacetals in a multicomponent manner. The reaction proceeded with high chemo/regioselectivity to yield 4-alkoxy-6-(4-aryl-1H-pyrrol-3-yl)pyrimidin-2-amines under milder conditions. It is found that α-aroylidineketene dithioacetals (2) undergo cycloaddition with (p-tolylsulfonyl)methyl isocyanide (3) [TosMIC], guanidine nitrate (5) and alcohol in the presence of NaH/THF to furnish the target 6-pyrrolylpyrimidines (8) in excellent yields.