How Lewis Acids Catalyze Ene Reactions

Research output: Contribution to JournalArticleAcademicpeer-review


The catalytic effect of various Lewis acids (LAs) on the ene reaction between propene (ene) and but-3-en-2-one (enophile) was studied quantum chemically using density functional theory and with coupled-cluster theory. The studied LAs efficiently accelerate the ene reaction by lowering the reaction barrier up to 12 kcal mol−1 compared to the uncatalyzed reaction. Our detailed activation strain and Kohn-Sham molecular orbital analyses reveal that coordination of a LA catalyst to the enophile decreases the reaction barrier of the ene reaction by inducing an asymmetry in the π-electronic system, which increases the asynchronicity and hence relieves the otherwise highly destabilizing activation strain and Pauli repulsion between the closed-shell filled π-orbitals of the ene and enophile. In all, these findings further demonstrate the generality of the Pauli-lowering catalysis concept.

Original languageEnglish
Pages (from-to)5275-5283
Number of pages9
JournalEuropean Journal of Organic Chemistry
Issue number37
Early online date12 Sep 2021
Publication statusPublished - 7 Oct 2021

Bibliographical note

Funding Information:
This work was supported by the Netherlands Organization for Scientific Research (NWO) and the Dutch Astrochemistry Network (DAN).

Publisher Copyright:
© 2021 The Authors. European Journal of Organic Chemistry published by Wiley-VCH GmbH

Copyright 2021 Elsevier B.V., All rights reserved.


  • Activation strain model
  • Density functional calculations
  • Ene reaction
  • Lewis acids
  • Reactivity


Dive into the research topics of 'How Lewis Acids Catalyze Ene Reactions'. Together they form a unique fingerprint.

Cite this