State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China.
University of Chinese Academy of Sciences, Beijing, 100049, China.
Angew Chem Int Ed Engl. 2020 Sep 1;59(36):15565-15569. doi: 10.1002/anie.202006383. Epub 2020 Jul 1.
A Mn-catalyzed diastereo- and enantioselective hydrogenation of α-substituted β-ketoamides has been realized for the first time under dynamic kinetic resolution conditions. anti-α-Substituted β-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.
首次在动态动力学拆分条件下实现了 Mn 催化的 α-取代的β-酮酰胺的非对映和对映选择性氢化。反式-α-取代的β-羟基酰胺是合成生物活性分子和手性药物的有用砌块，以高收率和优异的选择性（高达＞99%的 dr 和＞99%的 ee）和前所未有的高活性（TON 高达 10000）制备。通过 DFT 计算阐明了优异的立体选择性的起源。
