Document Type


Publication Date


Journal / Book Title

The Journal of Organic Chemistry


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.



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.