The relative configuration of the major diastereomer of 5a was determined by X-ray crystallographic analysis. 19b In conclusion, we have developed a domino annulation reaction of αoxo-β, γ-unsaturated ketones and malononitrile. The transition-metal free and extremely mild conditions, very short reaction time, simple procedure and excellent diastereoselectivity provide a novel and practical method for rapid assemble of polysubstituted tetrahydrocyclopenta [b]furanols.