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

Chemical Science Pub Date: 2012-01-26 DOI: 10.1039/C2SC00950A

Abstract

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.

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