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A facile and efficient one-pot synthesis of polyhydroquinoline derivatives via the Hantzsch reaction using a variety of aldehydes, 5,5-dimethyl-1,3-cyclohexanedione or 1,3-cyclohexanedione, ethyl acetoacetate, and ammonium acetate in the presence of potassium dodecatungstocobaltate trihydrate [K5CoW12O40. 3H2O] as a heterogeneous catalyst in a solvent-free media at 90 °C is described herein . The present methodology offers several advantages such as excellent yields, simple procedure, shorter reaction times (10-25 min.), milder conditions and the catalyst exhibited remarkable reusability.