A New Entry to Pd−H Chemistry:  Catalytic Asymmetric Conjugate Reduction of Enones with EtOH and a Highly Enantioselective Synthesis of Warfarin

[reaction: see text] We report here the catalytic asymmetric conjugate reduction of enones using ethanol as a hydride source. The reaction was carried out in the presence of a chiral Pd complex at ambient temperature in ethanol, and the desired products were obtained in high chemical yield and high enantioselectivity. We applied this novel reaction to the catalytic asymmetric synthesis of warfarin (96% ee), and on the basis of d-labeling experiments, the reaction mechanism is proposed.