Origins of the Endo and Exo Selectivities in Cyclopropenone, Iminocyclopropene, and Triafulvene Diels-Alder Cycloadditions

The Journal of Organic Chemistry
Brian J LevandowskiK N Houk

Abstract

The endo and exo stereoselectivities of Diels-Alder reactions of cyclopropenone, iminocyclopropene, and substituted triafulvenes with butadiene were rationalized using density functional theory calculations. When cyclopropenone is the dienophile, there is a 1.8 kcal/mol preference for the exo cycloaddition with butadiene, while the reaction of 3-difluoromethylene triafulvene with butadiene favors the endo cycloaddition by 2.8 kcal/mol. The influence of charge transfer and secondary orbital interactions on the stereoselectivity of Diels-Alder reactions involving triafulvenes and heteroanalogs is discussed. The predicted stereoselectivity correlates with both the charge and highest occupied molecular orbital (HOMO) coefficient at the C3 carbon of the triafulvene motif.

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Citations

Feb 20, 2019·Chemistry : a European Journal·Trevor A HamlinF Matthias Bickelhaupt
May 22, 2019·Chemistry : a European Journal·Ayush K NarsariaF Matthias Bickelhaupt
Dec 14, 2018·ChemistryOpen·Song YuF Matthias Bickelhaupt
Jan 11, 2019·Journal of Molecular Modeling·Brian J LevandowskiK N Houk
Jan 18, 2019·ChemistryOpen·Olatz Larrañaga, Abel de Cózar
Apr 15, 2021·Angewandte Chemie·Melissa RamirezKendall N Houk
May 16, 2019·The Journal of Organic Chemistry·Tyler K Heiss, Jennifer A Prescher
Jan 30, 2019·Journal of the American Chemical Society·Brian J LevandowskiK N Houk

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