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用于不对称亨利反应的基于配体的二聚体铬(III)-水杨醛络合物:碱金属离子络合促进的协同催化作用

Podand-based dimeric chromium(III)-salen complex for asymmetric Henry reaction: cooperative catalysis promoted by complexation of alkali metal ions.

作者信息

Ouyang Guang-Hui, He Yan-Mei, Fan Qing-Hua

机构信息

Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences (CAS), Beijing 100190 (P.R. China); Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300072 (P.R. China).

出版信息

Chemistry. 2014 Dec 8;20(50):16454-7. doi: 10.1002/chem.201404605. Epub 2014 Oct 24.

DOI:10.1002/chem.201404605
PMID:25346533
Abstract

A new kind of podand-based dimeric salen ligand was synthesized, and its association with potassium cations was investigated by (1) H NMR spectroscopy. The corresponding Cr(III) -salen dimer was assembled by a supramolecular host-guest self-assembly process and was then used as a catalyst in highly efficient and enantioselective asymmetric Henry reactions. Regulation by KBArF (BArF =[3,5-(CF3 )2 C6 H3 ]4 B) led to remarkable improvements in yield (by up to 58 %) and enantioselectivity (for example, from 80 % ee to 96 % ee).

摘要

合成了一种新型的基于开链多醚的二聚萨伦配体,并通过¹H NMR光谱研究了其与钾阳离子的缔合。相应的Cr(III)-萨伦二聚体通过超分子主客体自组装过程组装而成,然后用作高效对映选择性不对称亨利反应的催化剂。用KBArF(BArF = [3,5-(CF₃)₂C₆H₃]₄B)进行调控可使产率(提高高达58%)和对映选择性(例如,从80% ee提高到96% ee)得到显著改善。

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