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Issue 17, 2011
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Mechanism of intramolecular catalysis in the hydrolysis of alkyl monoesters of 1,8-naphthalic acid

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Abstract

Hydrolysis of alkyl 1,8-naphthalic acid monoesters 1a–d is subject to highly efficient intramolecular nucleophilic catalysis by the neighboring COOH group. The reactivity for the COOH reaction depends on the leaving group pKa, with values of βLG of −0.50, consistent with a mechanism involving rate determining breakdown of tetrahedral addition intermediates. The release of the steric strain of the peri-substitiuents in the highly reactive alkyl 1,8-naphthalic acid monoesters is fundamental to understand the observed special reactivity in this intramolecular reaction. DFT calculations show how the proton transfers involved in the cleavage of the neutral ester can be catalyzed by solvent water, thus facilitating the departure of poor alkoxide leaving groups.

Graphical abstract: Mechanism of intramolecular catalysis in the hydrolysis of alkyl monoesters of 1,8-naphthalic acid

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Article information


Submitted
11 Apr 2011
Accepted
03 Jun 2011
First published
06 Jun 2011

Org. Biomol. Chem., 2011,9, 6163-6170
Article type
Paper

Mechanism of intramolecular catalysis in the hydrolysis of alkyl monoesters of 1,8-naphthalic acid

B. S. Souza, S. F. Yunes, M. F. Lima, J. C. Gesser, M. M. Sá, H. D. Fiedler and F. Nome, Org. Biomol. Chem., 2011, 9, 6163
DOI: 10.1039/C1OB05574G

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