Catalytic Asymmetric Conjugate Reduction

Abstract Enantioselective reduction reactions are privileged transformations for the construction of trisubstituted stereogenic centers. While these include established synthetic strategies, such as asymmetric hydrogenation, methods based on the enantioselective addition of hydridic reagents to electrophilic prochiral substrates have also gained importance. In this context, the asymmetric conjugate reduction (ACR) of α,β‐unsaturated compounds has become a convenient approach for the synthesis of chiral compounds with trisubstituted stereocenters in α‐, β‐, or γ‐position to electron‐withdrawing functional groups. Because such activating groups are diverse and amenable of further derivatizations, ACRs provide a general and powerful synthetic entry towards a variety of valuable chiral building blocks. This Review provides a comprehensive collection of catalytic ACR methods involving transition‐metal, organic, and enzymatic catalysis since its first versions dating back to the late 1970s.