Mechanisms and Origins of Selectivities of the Lewis Acid-Catalyzed Diels-Alder Reactions between Arylallenes and Acrylates

The Journal of Organic Chemistry
Peiyuan YuK N Houk

Abstract

The mechanisms of recently reported Lewis acid-catalyzed Diels-Alder reactions of arylallenes and acrylates were studied using density functional theory calculations. A stepwise mechanism involving short-lived zwitterion intermediates is established. The reaction is endo-selective in the presence of Lewis acid catalyst. The [2 + 2] cycloaddition is not observed because of the greater charge separation in the first step of the [2 + 2] cycloaddition. The origins of chirality transfer in the Diels-Alder reaction using chiral arylallenes are uncovered, and the absolute stereochemistry of the product is predicted.

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Citations

Jan 17, 2020·Angewandte Chemie·Pascal VermeerenF Matthias Bickelhaupt
Mar 25, 2021·Accounts of Chemical Research·Trevor A HamlinIsrael Fernández

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