文献类型：期刊文献

英文题名：Conformational enantiodiscrimination for asymmetric construction of atropisomers

作者：Cen, Shouyi[1,2];Huang, Nini[1,2];Lian, Dongsheng[1,2];Shen, Ahui[1,2];Zhao, Mei-Xin[1,2];Zhang, Zhipeng[1,2]

机构：[1]East China Univ Sci & Technol, Frontiers Sci Ctr Materiobiol & Dynam Chem, Sch Chem & Mol Engn, Key Lab Adv Mat,Feringa Nobel Prize Scientist Joi, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Frontiers Sci Ctr Materiobiol & Dynam Chem, Sch Chem & Mol Engn, Feringa Nobel Prize Scientist Joint Res Ctr,Joint, Shanghai 200237, Peoples R China

年份：2022

卷号：13

期号：1

外文期刊名：NATURE COMMUNICATIONS

收录：;WOS:【SCI-EXPANDED(收录号:WOS:000840114800004)】；

基金：We thank the Research Center of Analysis and Test, East China University of Science and Technology for the help on the characterization, and Prof. Yifeng Chen (ECUST) for sharing the instruments. We thank Prof. Yuan-Yuan Zhu (HFUT) and Prof. Jie Sun (SIOC) for the help with single crystal X-ray diffraction and structure analysis. We acknowledge the National Natural Science Foundation of China (21702059), Fundamental Research Funds for the Central Universities (222201814014, JKVJ1211010, JKVJ12001010), Shanghai Pujiang Program (18PJ1402200), Shanghai Municipal Science and Technology Major Project (2018SHZDZX03), Program of Introducing Talents of Discipline to Universities (B16017) and the "Thousand Plan" Youth program for financial support.

语种：英文

摘要：Molecular conformations induced by the rotation about single bonds play a crucial role in chemical transformations. Revealing the relationship between the conformations of chiral catalysts and the enantiodiscrimination is a formidable challenge due to the great difficulty in isolating the conformers. Herein, we report a chiral catalytic system composed of an achiral catalytically active unit and an axially chiral 1,1 '-bi-2-naphthol (BINOL) unit which are connected via a C-O single bond. The two conformers of the catalyst induced by the rotation about the C-O bond, are determined via single-crystal X-ray diffraction and found to respectively lead to the formation of highly important axially chiral 1,1 '-binaphthyl-2,2 '-diamine (BINAM) and 2-amino-2 '-hydroxy-1,1 '-binaphthyl (NOBIN) derivatives in high yields (up to 98%), with excellent enantioselectivities (up to 98:2 e.r.) and opposite absolute configurations. The results highlight the importance of conformational dynamics of chiral catalysts in asymmetric catalysis. Molecular flexiblity and conformational dynamics of chiral catalysts are not often taken into account in models of enantiodiscrimination. Here the authors design a catalytic system in which two conformers of the same catalyst can lead to axially chiral products of opposite absolute configurations.