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The reaction of isodehydracetic acid with amines was serendipitously found to afford β-enaminones in the presence of the coupling agent 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC). Under the optimal reaction condition, 23 examples of α-aminomethylene glutaconic anhydride were obtained at approximately 30−80% yields. This is a concise, operationally simple method to expediently synthesize a new type of β-enaminone-containing compound.