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Intramolecular general acid catalysis in the aminolysis of β-lactam antibiotics

Llinas, Antonio and Page, Michael I. (2004) Intramolecular general acid catalysis in the aminolysis of β-lactam antibiotics. Organic and Biomolecular Chemistry, 2. pp. 651-654. ISSN 1477-0539

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Abstract

The rate of aminolysis of benzylpenicillin and cephaloridine by hydroxylamine, unlike other amines, shows only a first order dependence on amine concentration. The rate enhancement compared with that predicted from a Bronsted plot for other primary amines with benzylpenicillin is greater than 106. This is much more than an -effect and is compatible with rate-limiting formation of the tetrahedral intermediate due to a rapid intramolecular general acid catalysed breakdown of the intermediate. For cephaloridine, the rate enhancement is greater than 104 which demonstrates that -lactam C–N bond fission and expulsion of the leaving group at C3 are not concerted.

Item Type: Article
Subjects: Q Science > Q Science (General)
Q Science > QD Chemistry
Schools: School of Applied Sciences
School of Applied Sciences > Biomolecular Sciences Research Centre
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References:

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Depositing User: Sara Taylor
Date Deposited: 08 Feb 2008 14:37
Last Modified: 20 Oct 2008 10:06
URI: http://eprints.hud.ac.uk/id/eprint/517

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