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The highly enantioselective Michael addition of 1,3-cyclic dicarbonyl compounds to α,β-unsaturated ketones was reported to be catalyzed by an organic primary amine derived from quinine. A chiral anticoagulant drug, (S)-warfarin, was directly prepared in 96% ee, and other related important adducts were also obtained in excellent enantioselectivity (89−99% ee).