How Alkali Cations Catalyze Aromatic Diels-Alder Reactions

Pascal Vermeeren, Francine Brinkhuis, Trevor A. Hamlin*, F. Matthias Bickelhaupt

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review


We have quantum chemically studied alkali cation-catalyzed aromatic Diels-Alder reactions between benzene and acetylene forming barrelene using relativistic, dispersion-corrected density functional theory. The alkali cation-catalyzed aromatic Diels-Alder reactions are accelerated by up to 5 orders of magnitude relative to the uncatalyzed reaction and the reaction barrier increases along the series Li+ < Na+ < K+ < Rb+ < Cs+ < none. Our detailed activation strain and molecular-orbital bonding analyses reveal that the alkali cations lower the aromatic Diels-Alder reaction barrier by reducing the Pauli repulsion between the closed-shell filled orbitals of the dienophile and the aromatic diene. We argue that such Pauli mechanism behind Lewis-acid catalysis is a more general phenomenon. Also, our results may be of direct importance for a more complete understanding of the network of competing mechanisms towards the formation of polycyclic aromatic hydrocarbons (PAHs) in an astrochemical context.

Original languageEnglish
Pages (from-to)1167-1174
Number of pages8
JournalChemistry - An Asian Journal
Issue number7
Early online date3 Feb 2020
Publication statusPublished - 1 Apr 2020


  • Activation Strain Model
  • Alkali Cation
  • Aromatic Diels-Alder Reaction
  • Density Functional Calculations
  • Reactivity


Dive into the research topics of 'How Alkali Cations Catalyze Aromatic Diels-Alder Reactions'. Together they form a unique fingerprint.

Cite this