N-alkylpyrimidinium cations carrying a dienophilic side-chain at the 2-or 5-position undergo intramolecular inverse electron demand Diels-Alder reactions into the corresponding annelated pyridine derivatives under considerably milder conditions than the corresponding neutral pyrimidines. Protonation of the pyrimidine ring also facilitates the intramolecular Diels-Alder reaction. Protonation of less activated pyrimidines leads, however, to products ...