Document Type
Article
Publication Date
7-7-2017
Journal / Book Title
The Journal of Organic Chemistry
Abstract
Nitrofurans undergo intramolecular Diels-Alder reactions with tethered electron-poor dienophiles more rapidly and in higher yield than non-nitrated furans. Computational studies indicate that increased stabilization of a partial positive charge on the nitro-substituted carbon in both transition state and product is the driving force for these reactions. Frontier molecular orbital energy differences indicate a switch from normal to inverse electron demand upon nitration. There does not appear to be a contribution from any differences in aromatic stabilization energy between furans and nitrofurans. Calculations show that the nitrofuran reactions proceed via a highly asynchronous transition state allowing easier bond formation between two sterically hindered carbons.
DOI
10.1021/acs.joc.7b00781
MSU Digital Commons Citation
Cowie, Thomas Y.; Veguillas, Marcos; Rae, Robert L.; Rougé, Mathilde; Zurek, Justyna M.; Prentice, Andrew W.; Paterson, Martin J.; and Bebbington, Magnus, "Intramolecular Nitrofuran Diels-Alder Reactions: Extremely Substituent-Tolerant Cycloadditions Via Asynchronous Transition States" (2017). Department of Chemistry and Biochemistry Faculty Scholarship and Creative Works. 209.
https://digitalcommons.montclair.edu/chem-biochem-facpubs/209
Published Citation
Cowie, T. Y., Veguillas, M., Rae, R. L., Rougé, M., Zurek, J. M., Prentice, A. W., ... & Bebbington, M. W. (2017). Intramolecular Nitrofuran Diels–Alder Reactions: Extremely Substituent-Tolerant Cycloadditions via Asynchronous Transition States. The Journal of Organic Chemistry, 82(13), 6656-6670.