The simplest Diels-Alder reactions are not endo-selective.

Chemical Science
William J LordingMichael N Paddon-Row

Abstract

There is a widespread perception that the high level of endo selectivity witnessed in many Diels-Alder reactions is an intrinsic feature of the transformation. In contrast to expectations based upon this existing belief, the first experimental Diels-Alder reactions of a novel, deuterium-labeled 1,3-butadiene with commonly used mono-substituted alkenic dienophiles (acrolein, methyl vinyl ketone, acrylic acid, methyl acrylate, acrylamide and acrylonitrile) reveal kinetic endo : exo ratios close to 1 : 1. Maleonitrile, butenolide, α-methylene γ-butyrolactone, and N-methylmaleimide behave differently, as does methyl vinyl ketone under Lewis acid catalysis. CBS-QB3 calculations incorporating solvent and temperature parameters give endo : exo product ratios that are in near quantitative agreement with these and earlier experimental findings. This work challenges the preconception of innate endo-selectivity by providing the first experimental evidence that the simplest Diels-Alder reactions are not endo-selective. Trends in behaviour are traced to steric and electronic effects in Diels-Alder transition structures, giving new insights into these fundamental processes.

References

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Jan 17, 2020·Angewandte Chemie·Pascal VermeerenF Matthias Bickelhaupt

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Citations

Apr 15, 2021·Angewandte Chemie·Melissa RamirezKendall N Houk
May 25, 2021·International Journal of Pharmaceutics·Adeolu Oluwasanmi, Clare Hoskins
Jun 11, 2021·The Journal of Organic Chemistry·Yining Lu, Dean J Tantillo

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