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

A Mn-catalyzed diastereo- and enantioselective hydrogenation of alpha-substituted beta-ketoamides has been realized for the first time under dynamic kinetic resolution conditions. anti-alpha-Substituted beta-hydroxy amides, which are useful building blocks for the synthesis of bioactive molecules and chiral drugs, were prepared in high yields with excellent selectivity (up to > 99 % dr and > 99 % ee) and unprecedentedly high activity (TON up to 10000). The origin of the excellent stereoselectivity was clarified by DFT calculations.