The mechanisms of the cascade reactions of amino-substituted imidazoles, pyrroles, and pyrazoles with 1,3,5-triazines have been studied using first principle MP2/6-311++G**//B3LYP/6-31G* calculations in both the gas phase and solution. Calculations indicate that these cascade reactions start with stepwise inverse-electron demand Diels-Alder (IDA) reactions, followed by elimination of ammonia from the IDA adducts, and retro Diels-Alder (RDA) reactions (referred as to the IER path). An alternative IRE path involving a reaction sequence of IDA, RDA, and elimination of ammonia is ruled out since the RDA transition states in this pathway are higher in energy than the reactants by as much as 50 kcal/mol. The preference of the IER over the IRE path is discussed.