Dienophile twisting and substituent effects influence reaction rates of intramolecular Diels-Alder cycloadditions

A DFT study

Kelli S. Khuong, Chris M. Beaudry, Dirk Trauner, K. N. Houk

Research output: Contribution to journalArticle

Abstract

Intramolecular cycloadditions of 5-vinyl-1,3-cyclohexadienes were studied with B3LYP/6-31G(d) density functional calculations. The one-atom tether dictates that the Z substituent becomes exo and the E substituent becomes endo in the TS. The geometry of the cycloaddition TS is typical of a pericyclic transformation except unusual twisting of the dienophile places the endo substituent in a relatively steric-free position and the exo substituent in a highly crowded position. The experimental rate differences between isomeric pairs of vinylcyclohexadienes can be explained by comparing reactant destabilization when a bulky group occupies the Z position of the starting alkene and transition state stabilization when a bulky group is endo in the cycloaddition TS.

Original languageEnglish (US)
Pages (from-to)3688-3689
Number of pages2
JournalJournal of the American Chemical Society
Volume127
Issue number11
DOIs
StatePublished - Mar 23 2005

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Cycloaddition
Cycloaddition Reaction
Discrete Fourier transforms
Reaction rates
Alkenes
Olefins
Density functional theory
Stabilization
Atoms
Geometry

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Dienophile twisting and substituent effects influence reaction rates of intramolecular Diels-Alder cycloadditions : A DFT study. / Khuong, Kelli S.; Beaudry, Chris M.; Trauner, Dirk; Houk, K. N.

In: Journal of the American Chemical Society, Vol. 127, No. 11, 23.03.2005, p. 3688-3689.

Research output: Contribution to journalArticle

Khuong, Kelli S. ; Beaudry, Chris M. ; Trauner, Dirk ; Houk, K. N. / Dienophile twisting and substituent effects influence reaction rates of intramolecular Diels-Alder cycloadditions : A DFT study. In: Journal of the American Chemical Society. 2005 ; Vol. 127, No. 11. pp. 3688-3689.
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