Document Type
Postprint
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
Montclair State University 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
Rights
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Organic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/acs.joc.7b00781