Manganese‐Catalyzed anti‐Selective Asymmetric Hydrogenation of α‐Substituted β‐Ketoamides

: A Mn-catalyzed diastereo- and enantioselective hydrogenation of α-substituted β-ketoamides has been realized for the first time under dynamic kinetic resolution conditions. The anti-α-substituted β-hydroxy amides, a type of useful building blocks for synthesis of bioactive molecules and chiral drugs, have been prepared in high yields with excellent selectivities (up to >99% dr and >99% ee) and unprecedentedly high activity (TON up to 10000). The origin of excellent stereoselectivities has been clarified by DFT calculation study on the structures and the corresponding energies of the transition states possibly involved in the catalysis.