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 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.

Keywords

• cycloaddition
• Diels–Alder
• furan
• structure-energy correlation