Intramolecular Nitrofuran Diels-Alder Reactions: Extremely Substituent-Tolerant Cycloadditions via Asynchronous Transition States

Thomas Y. Cowie, Marcos Veguillas, Robert L. Rae, Mathilde Rougé, Justyna M. Zurek, Andrew W. Prentice, Martin J. Paterson, Magnus W.P. Bebbington

Research output: Contribution to journalArticle

3 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)6656-6670
Number of pages15
JournalJournal of Organic Chemistry
Volume82
Issue number13
DOIs
StatePublished - 7 Jul 2017

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Nitrofurans
Cycloaddition
Furans
Carbon
Stabilization
Nitration
Electrons
Molecular orbitals
Switches

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Cowie, Thomas Y. ; Veguillas, Marcos ; Rae, Robert L. ; Rougé, Mathilde ; Zurek, Justyna M. ; Prentice, Andrew W. ; Paterson, Martin J. ; Bebbington, Magnus W.P. / Intramolecular Nitrofuran Diels-Alder Reactions : Extremely Substituent-Tolerant Cycloadditions via Asynchronous Transition States. In: Journal of Organic Chemistry. 2017 ; Vol. 82, No. 13. pp. 6656-6670.
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Intramolecular Nitrofuran Diels-Alder Reactions : Extremely Substituent-Tolerant Cycloadditions via Asynchronous Transition States. / Cowie, Thomas Y.; Veguillas, Marcos; Rae, Robert L.; Rougé, Mathilde; Zurek, Justyna M.; Prentice, Andrew W.; Paterson, Martin J.; Bebbington, Magnus W.P.

In: Journal of Organic Chemistry, Vol. 82, No. 13, 07.07.2017, p. 6656-6670.

Research output: Contribution to journalArticle

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