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

Linli Zhang; Zheng Wang; Zhaobin Han; Kuiling Ding

doi:10.1002/anie.202006383

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

Angew Chem Int Ed Engl. 2020 Sep 1;59(36):15565-15569. doi: 10.1002/anie.202006383. Epub 2020 Jul 1.

Authors

Linli Zhang¹, Zheng Wang¹, Zhaobin Han¹, Kuiling Ding^{1

2

3}

Affiliations

¹ 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.
² University of Chinese Academy of Sciences, Beijing, 100049, China.
³ Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240, China.

PMID: 32449804
DOI: 10.1002/anie.202006383

Abstract

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.

Keywords: PNN ligands; asymmetric catalysis; hydrogenation; manganese; β-hydroxy amides.

Publication types

Research Support, Non-U.S. Gov't