Dual Activation of Aromatic Diels–Alder Reactions

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

The unusually fast Diels–Alder reactions of [5]cyclophanes were analyzed by DFT at the BLYP-D3(BJ)/TZ2P level of theory. The computations were guided by an integrated activation-strain and Kohn–Sham molecular orbital analysis. It is revealed why both [5]metacyclophane and [5]paracyclophane exhibit a significant rate enhancement compared to their planar benzene analogue. The activation strain analyses revealed that the enhanced reactivity originates from 1) predistortion of the aromatic core resulting in a reduced activation strain of the aromatic diene, and/or 2) enhanced interaction with the dienophile through a distortion-controlled lowering of the HOMO–LUMO gap within the diene. Both of these physical mechanisms and thus the rate of Diels–Alder cycloaddition can be tuned through different modes of geometrical distortion (meta versus para bridging) and by heteroatom substitution in the aromatic ring. Judicious choice of the bridge and heteroatom in the aromatic core enables effective tuning of the aromatic Diels–Alder reactivity to achieve activation barriers as low as 2 kcal mol−1, which is an impressive 35 kcal mol−1 lower than that of benzene.

Original languageEnglish
Pages (from-to)9902-9912
Number of pages11
JournalChemistry - A European Journal
Volume25
Issue number42
Early online date21 May 2019
DOIs
Publication statusPublished - 25 Jul 2019

Fingerprint

Chemical activation
Benzene
Cycloaddition
Molecular orbitals
Discrete Fourier transforms
Substitution reactions
Tuning

Keywords

  • activation strain model
  • arenes
  • cycloaddition
  • cyclophanes
  • density functional calculations

Cite this

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title = "Dual Activation of Aromatic Diels–Alder Reactions",
abstract = "The unusually fast Diels–Alder reactions of [5]cyclophanes were analyzed by DFT at the BLYP-D3(BJ)/TZ2P level of theory. The computations were guided by an integrated activation-strain and Kohn–Sham molecular orbital analysis. It is revealed why both [5]metacyclophane and [5]paracyclophane exhibit a significant rate enhancement compared to their planar benzene analogue. The activation strain analyses revealed that the enhanced reactivity originates from 1) predistortion of the aromatic core resulting in a reduced activation strain of the aromatic diene, and/or 2) enhanced interaction with the dienophile through a distortion-controlled lowering of the HOMO–LUMO gap within the diene. Both of these physical mechanisms and thus the rate of Diels–Alder cycloaddition can be tuned through different modes of geometrical distortion (meta versus para bridging) and by heteroatom substitution in the aromatic ring. Judicious choice of the bridge and heteroatom in the aromatic core enables effective tuning of the aromatic Diels–Alder reactivity to achieve activation barriers as low as 2 kcal mol−1, which is an impressive 35 kcal mol−1 lower than that of benzene.",
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Dual Activation of Aromatic Diels–Alder Reactions. / Narsaria, Ayush K.; Hamlin, Trevor A.; Lammertsma, Koop; Bickelhaupt, F. Matthias.

In: Chemistry - A European Journal, Vol. 25, No. 42, 25.07.2019, p. 9902-9912.

Research output: Contribution to JournalArticleAcademicpeer-review

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