Issue 15, 2016

Supramolecular phosphate transfer catalysis by pillar[5]arene

Abstract

A kinetic study on dinitrophenylphosphate monoester hydrolysis in the presence of a cationic pillararene, P5A, has been carried out. Formation of the supramolecular complex between phosphate ester and P5A has been studied by NMR showing complexation-induced upfield proton shifts indicative of aromatic ring inclusion in the pillararene cavity. Molecular dynamic calculations allow structure characterization for the 1 : 1 and 1 : 2 complexes. As a result of the supramolecular interaction both the acidity of DNPP and its hydrolysis rate constants are increased. Catalysis results from combination of both electrostatic stabilization reducing the negative electron density on the PO3= oxygens and monoester dianion destabilization by the steric effects of close NMe3+ groups hindering the hydrogen-bonding with water and destabilising the monoester dianion.

Graphical abstract: Supramolecular phosphate transfer catalysis by pillar[5]arene

Supplementary files

Article information

Article type
Communication
Submitted
15 Dec 2015
Accepted
18 Jan 2016
First published
18 Jan 2016

Chem. Commun., 2016,52, 3167-3170

Author version available

Supramolecular phosphate transfer catalysis by pillar[5]arene

D. G. Liz, A. M. Manfredi, M. Medeiros, R. Montecinos, B. Gómez-González, L. Garcia-Rio and F. Nome, Chem. Commun., 2016, 52, 3167 DOI: 10.1039/C5CC10214F

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