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Amide bond cleavage: acceleration due to a 1,3-diaxial interaction with a carboxylic acid.

ABSTRACT: To independently assess the contribution of ground-state pseudoallylic strain to the enormous rates of amide bond cleavage in tertiary amide derivatives of Kemp's triacid, we have studied four amide derivatives of (1alpha-3alpha-5beta)-5-tert-butyl-1,3-cyclohexanedicarboxylic acid. Our results demonstrate that absent pseudoallylic strain, a 1,3-diaxial interaction of an amide with a carboxylic acid leads to only a 2400-fold increase in the rate of amide bond cleavage as compared with the rate of hydrolysis of an unactivated peptide bond.

SUBMITTER: Gerschler JJ

PROVIDER: S-EPMC2518966 | biostudies-literature | 2007 Jan

REPOSITORIES: biostudies-literature

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Amide bond cleavage: acceleration due to a 1,3-diaxial interaction with a carboxylic acid.

Gerschler Jared J JJ Wier Kevin A KA Hansen David E DE

The Journal of organic chemistry 20070101 2

To independently assess the contribution of ground-state pseudoallylic strain to the enormous rates of amide bond cleavage in tertiary amide derivatives of Kemp's triacid, we have studied four amide derivatives of (1alpha-3alpha-5beta)-5-tert-butyl-1,3-cyclohexanedicarboxylic acid. Our results demonstrate that absent pseudoallylic strain, a 1,3-diaxial interaction of an amide with a carboxylic acid leads to only a 2400-fold increase in the rate of amide bond cleavage as compared with the rate of ...[more]

PMID: 17221991

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