The reaction of (perfluoroalkyl)furan-3(2H)-ones and β-diketone containing an acetal moiety with (hetero)aromatic 1,2-diamines was studied. Quinoxalines and pyrido[3,4-b]pyrazine bearing the enaminoketone fragment were ynthesized by the regioselective addition of a dinucleophile at the α-dicarbonyl moiety of polyketones. In the case of β-diketone containing acetal and ester groups, the conversion involves the α-ketoester moiety to form a quinoxalinyl-substituted 2,3-butanedione. All products were characterized by NMR spectroscopy and X-ray diffraction. © 2023, Pleiades Publishing, Ltd.