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

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 found for intermolecular Diels-Alder reactions.