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Unusual structure-energy correlations in intramolecular Diels-Alder reaction transition states.

ABSTRACT: Detailed analysis of calculated data from an experimental/computational study of intramolecular furan Diels-Alder reactions has led to the unusual discovery that the mean contraction of the newly forming C-C ?-bonds from the transition state to the product shows a linear correlation with both reaction Gibbs free energies and reverse energy barriers. There is evidence for a similar correlation in other intramolecular Diels-Alder reactions involving non-aromatic dienes. No such correlation is found for intermolecular Diels-Alder reactions.

SUBMITTER: Zurek JM

PROVIDER: S-EPMC6272020 | biostudies-literature | 2014 Sep

REPOSITORIES: biostudies-literature

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Unusual structure-energy correlations in intramolecular Diels-Alder reaction transition states.

Zurek Justyna M JM Rae Robert L RL Paterson Martin J MJ Bebbington Magnus W P MW

Molecules (Basel, Switzerland) 20140929 10

Detailed analysis of calculated data from an experimental/computational study of intramolecular furan Diels-Alder reactions has led to the unusual discovery that the mean contraction of the newly forming C-C σ-bonds from the transition state to the product shows a linear correlation with both reaction Gibbs free energies and reverse energy barriers. There is evidence for a similar correlation in other intramolecular Diels-Alder reactions involving non-aromatic dienes. No such correlation is foun ...[more]

PMID: 25268713

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