A synthetic route to benzopyrano [3, 4-b] pyazines and the first reported synthesis of the pyrazino [2, 3-c] quinoline system are described whereby the fused pyrazine ring is constructed by an intramolecular nitrile/l, 2, 4-triazine Diels-Alder cycloaddition. Unsuccessful efforts to access thieno [2, 34] pyrazines by an analogous strategy are detailed.