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Issue 10, 2002
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Concurrent nucleophilic and general acid catalysis of the hydrolysis of a phosphate triester

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Abstract

The hydrolysis of diethyl 8-dimethylaminonaphthyl-1-phosphate is catalysed by the neighbouring dimethylammonium group, with a rate acceleration, compared with diethyl naphthyl-1-phosphate, of almost 106. The effective pKa of the naphtholate leaving group is reduced from 9.4 to 3.4 by partial protonation in the transition state. The reaction is catalysed by oxyanion nucleophiles, and it is shown that a common nucleophilic mechanism, enhanced by general acid catalysis by the neighbouring dimethylammonium group, accounts for all the observed reactions. The efficiency of general acid catalysis depends on the extent of negative charge development on the leaving group oxygen in the transition state for P–O cleavage, and the strength of the intramolecular hydrogen bond in reactant and transition state.

Graphical abstract: Concurrent nucleophilic and general acid catalysis of the hydrolysis of a phosphate triester

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Article information


Submitted
14 May 2002
Accepted
05 Aug 2002
First published
28 Aug 2002

J. Chem. Soc., Perkin Trans. 2, 2002, 1708-1712
Article type
Paper

Concurrent nucleophilic and general acid catalysis of the hydrolysis of a phosphate triester

N. Asaad and A. J. Kirby, J. Chem. Soc., Perkin Trans. 2, 2002, 1708
DOI: 10.1039/B204609A

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