Catalytically active supramolecular porphyrin boxes: acceleration of the methanolysis of phosphate triesters via a combination of increased local nucleophilicity and reactant encapsulation

被引：39

作者：

Kang, Byungman

Kurutz, Josh W.

Youm, Kyoung-Tae

Totten, Ryan K.

Hupp, Joseph T. ^{[1
]}

Nguyen, SonBinh T.

机构：

[1] Northwestern Univ, Dept Chem, Evanston, IL 60208 USA

来源：

CHEMICAL SCIENCE | 2012年 / 3卷 / 06期

关键词：

ARTIFICIAL ENZYMES; OLEFIN METATHESIS; MOLECULAR RECOGNITION; NMR-SPECTROSCOPY; HYDROLYSIS; COMPLEXES; CATALYSIS; MECHANISM; METALLOPORPHYRINS; POLYMERIZATION;

D O I：

10.1039/c2sc00950a

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Box-like tetrakis(metalloporphyrin) supramolecular assemblies possessing Zn and Al metal sites can catalyze the methanolysis of phosphate triesters with a high rate enhancement, up to 430 times faster than the uncatalyzed reaction. Mechanistic studies suggest that the observed rate enhancement can be attributed to a high local concentration of methoxide ion that operates in concert with a solvophobically driven encapsulation of substrates by the porphyrinic assembly.

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页码：1938 / 1944

页数：7

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