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Please use this identifier to cite or link to this item: http://hdl.handle.net/123456789/12899

Title: Diels-Alder cycloaddition versus ring-opening esterification: A computational study of the mechanism of formation of oxa-norbonene lactones from the reaction of furfuryl alcohol and itaconic anhydride
Authors: Fosu, Evans
Botchway, Cecil Humphrey
Tia, Richard
Adei, Evans
Issue Date: 30-May-2018
Publisher: Elsevier B.V.
Abstract: The reactions of furfuryl alcohol with itaconic anhydride can proceed via four plausible pathways – two pathways involving initial Diels-Alder cycloaddition followed by lactonization and two pathways involving initial esterification followed by intramolecular Diels-Alder cycloaddition – to afford two distinct norbornene products bearing either a five- or six-membered butyrolactone ring respectively. DFT calculations reported herein show that the first-step Diels-Alder cycloaddition reactions have barriers of 8.5 and 11.8 kcal/mol which are far lower than the barriers of 29.6 and 36.9 kcal/mol for the esterification pathways. The calculated energies for the experimentally observed five- and six membered oxa-norbornene lactone isomers are exergonic with reaction energies of −17.1 and −12.8 kcal/mol respectively. Thermodynamically the five-membered isomer is more stable adduct than the six-membered adduct. Thus the most preferred pathway is the one involving initial [4 + 2] cycloaddition followed by lactonization to form the five-membered butylrolactone ring. Substitution of methyl groups on the carbon bearing the hydroxyl group shows that the substituents do not affects the reaction pathways markedly.
Description: An article published by Elsevier B.V. and also available at https://doi.org/10.1016/j.comptc.2018.05.019
URI: http://hdl.handle.net/123456789/12899
Appears in Collections:College of Science

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