Intramolecular Nitrofuran Diels-Alder reactions: extremely substituent-tolerant cycloadditions from asynchronous transition states

Thomas Y. Cowie, Marcos Veguillas Hernando, Robert L. Rae, Mathilde Rougé, Justyna Marlena Zurek, Andrew W. Prentice, Martin J. Paterson, Magnus William Paul Bebbington

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Abstract

Nitrofurans undergo intramolecular Diels-Alder reactions with tethered electron-poor dienophiles more rapidly and in higher yields 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.
Original languageEnglish
Pages (from-to)6656-6670
Number of pages15
JournalJournal of Organic Chemistry
Volume82
Issue number13
Early online date2 Jun 2017
DOIs
Publication statusPublished - 7 Jul 2017

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    Cowie, T. Y., Veguillas Hernando, M., Rae, R. L., Rougé, M., Zurek, J. M., Prentice, A. W., Paterson, M. J., & Bebbington, M. W. P. (2017). Intramolecular Nitrofuran Diels-Alder reactions: extremely substituent-tolerant cycloadditions from asynchronous transition states. Journal of Organic Chemistry, 82(13), 6656-6670. https://doi.org/10.1021/acs.joc.7b00781