A viable one-pot synthesis of challenging 4H- [3,4-c]quinolone-4,5(6H)-diones by the reaction of β-(2-aminophenyl)-α,β-ynones with ethyl malonyl chloride is described. Their further elaboration in the presence of an excess of 40 % methyl amine aqueous solution in EtOH gives the benzo[c][2,7]naphthyridine-4,5(3H,6H)-diones of pharmacological interest in high yields.The product selectivity control of the divergent sequential condensation/C-annulation/intramolecular transesterification vs condensation/O-annulation/ring opening reactions of β-(2-aminophenyl)-α,β-ynones with malonyl chloride under metal free conditions has been addressed.