Supramolecular synthesis of coumarin derivatives catalyzed by a coordination-assembled cage in aqueous solution

论文摘要

A self-assembled Pd4L2 cage is employed as a water-soluble molecular flask for the synthesis of functionalized coumarins from a series of salicylaldehyde derivatives and cyanoacetates/malononitrile. The catalytic reaction features mild aqueous conditions and broad substrate scope. Crystal structures of the host-guest complexes for two substrates and one analogous intermediate have been obtained, shedding light on the supramolecular reaction mechanism. Michaelis-Menten kinetic studies were performed in one typical case, revealing that the rate of product formation has been enhanced by over 23-fold in contrast to the background reaction without cage. Moreover, the same reaction catalyzed by a smaller Pd6L4 cage gives a mixture of products and much lower yields, suggesting that fine-tuning on the size and symmetry of the cages’ cavity is crucial for their applications in supramolecular catalysis.

论文目录

• 1 Introduction
• 2 Experimental
•   2.1 General information
•   2.2 Synthesis and characterization of cage 1 and cou-marin 4aa
• 3 Results and discussion
•   3.1 Substrate scope
•   3.2 Cavity size effect
•   3.3 Inhibition experiment
•   3.4 Michaelis-Menten kinetics
•   3.5 Mechanistic studies
• 4 Conclusions

文章来源

类型: 期刊论文

作者: Shao-Chuan Li,Li-Xuan Cai,Li-Peng Zhou,Fang Guo,Qing-Fu Sun

来源: Science China(Chemistry) 2019年06期

年度: 2019

分类: 工程科技Ⅰ辑

专业: 化学

单位: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences,College of Chemistry, Liaoning University

基金: supported by the National Natural Science Foundation of China (21825107,21601183,21801241,21571090),Natural Science Foundation of Fujian Province (2016J05051,2017J05037),the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB20000000)

分类号: O641.4;O643.36

页码: 713-718

总页数: 6

文件大小: 5568K

下载量: 19