Issue 5, 2005

Theoretical study of the o-OH participation in catechol ester ammonolysis

Abstract

The possible catalytic effect of the vicinal hydroxyl group during the ammonolysis of acetylcatechol has been studied by first principle calculations. A very efficient intramolecular catalysis was found to occur when the catechol ester o-OH group is deprotonated: the activation energy of the ammonolysis decreases by 24 kcal mol−1 as compared to that of acetylphenol ammonolysis. Using this value, the o-oxyanion-catalysed intramolecular ammonolysis was estimated to be orders of magnitude faster than the ammonolysis of acetylphenol or nonionised acetylcatechol. The analogy with the aminolysis of peptidyl-tRNA that occurs during protein biosynthesis implies several orders of magnitude acceleration due to complete or partial deprotonation of its 3′-terminal adenosine 2′-OH providing a mechanistic possibility for general acid–base catalysis by the ribosome.

Graphical abstract: Theoretical study of the o-OH participation in catechol ester ammonolysis

Article information

Article type
Paper
Submitted
12 Nov 2004
Accepted
11 Jan 2005
First published
03 Feb 2005

Org. Biomol. Chem., 2005,3, 737-744

Theoretical study of the o-OH participation in catechol ester ammonolysis

M. A. Rangelov, G. N. Vayssilov, V. M. Yomtova and D. D. Petkov, Org. Biomol. Chem., 2005, 3, 737 DOI: 10.1039/B417285J

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