Malononitrile‐Assisted Highly Chemoselective Bismuth Triflate Catalyzed Conjugate Reduction of α,β‐Unsaturated Ketones

A very simple, direct, bismuth‐catalyzed conjugate reduction protocol that allows for the catalytic regioselective formation of substituted ketones from enones under mild conditions has been developed. We have shown for the first time that the combined poly(methylhydro)siloxane‐malononitrile system can serve as an efficient reductant/reagent in 1,4‐conjugate reduction of enones. The regioselectivity, efficiencies, and experimental simplicity of the present method complements the more complex methods previously employed in copper or palladium‐catalyzed reduction. This method should prove attractive because of its mild reaction conditions and the interesting chemistry of combining the use of poly(methylhydro)siloxane and malononitrile for selective reduction.