Unusual Structure-Energy Correlations in Intramolecular Diels–Alder Reaction Transition States

Molecules

Justyna M. Żurek²  Robert L. Rae²  Martin J. Paterson¹  Magnus W. P. Bebbington¹ 

[1] id="af1-molecules-19-15535">Institute of Chemical Science, School of Engineering and Physical Sciences, William Perkin building, Heriot-Watt University, Edinburgh EH14 4AS,

关键词: cycloaddition;    Diels–Alder;    furan;    structure-energy correlation;   

DOI  :  10.3390/molecules191015535

来源: mdpi

【 摘 要 】

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.

【 授权许可】

CC BY   
© 2014 by the authors; licensee MDPI, Basel, Switzerland.