In this paper we report an unexpected synthesis of the 2,3,4‐trisubstituted quinoline systems. The reaction between imino‐isatin (synthesized from the reaction of isatin and ammonia (2 M in MeOH)) and dialkylacetylenedicarboxylates proceeds in MeOH at room temperature in the presence of pyridine as an organocatalyst. The structures of all new compounds were corroborated spectroscopically (1H‐ and 13C‐NMR, and elemental analysis). A plausible mechanism for this type of reaction is proposed.