Intramolecular Diels-Alder reaction in enyne-allenes: A computational investigation and comparison with the Myers-Saito and Schmittel reactions

Hsin Tsung Chen, Hui Lung Chen, Jia-Jen Ho

Research output: Contribution to journalArticle

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Abstract

The reaction mechanisms as well as substituted effect and solvent effect of the enyne-allenes are investigated by Density Functional Theory (DFT) method and compared with the Myers-Saito and Schmittel reactions. The Myers-Saito reaction of non-substituted enyne-allenes is kinetically and thermodynamically favored as compared to the Schmittel reaction; while the concerted [4 + 2] cycloaddition is only 1.32 kcal/mol higher than the C 2 -C 7 cyclization and more exothermic (δ R E = -69.38 kcal/mol). For R1=CH 3 and t-Bu, the increasing barrier of the C 2 -C 7 cyclization is higher than that for the C 2 -C 6 cyclization because of the steric effect, so the increased barrier of the [4 + 2] cycloaddition is affected by such substituted electron-releasing group. Moreover, the strong steric effect of R 1 = t-Bu would shift the C 2 -C 7 cyclization to the [4 + 2] cycloaddition. On the other hand, for R 1 =Ph, NH 2 , O - , NO 2 , and CN substituents, the barrier of the C 2 -C 6 cyclization would be more diminished than the C 2 -C 7 cyclization due to strong mesomeric effect; the reaction path of C 2 -C 7 cyclization would also shift to the [4 + 2] cycloaddition. The solvation does not lead to significant changes in the potential-energy surface of the reaction except for the more polar surrounding solvent such as dimethyl sulfoxide (DMSO), or water.

Original languageEnglish
Pages (from-to)134-140
Number of pages7
JournalJournal of Physical Organic Chemistry
Volume23
Issue number2
DOIs
Publication statusPublished - 2010 Feb 1

Fingerprint

Diels-Alder reactions
Cyclization
cycloaddition
Cycloaddition
shift
releasing
Potential energy surfaces
Solvation
solvation
Dimethyl Sulfoxide
propadiene
Density functional theory
potential energy
methylidyne
density functional theory
Electrons
Water
water
electrons

Keywords

  • DFT
  • Diels-Alder reaction
  • Enyne-allenes
  • Myers-Saito

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry

Cite this

Intramolecular Diels-Alder reaction in enyne-allenes : A computational investigation and comparison with the Myers-Saito and Schmittel reactions. / Chen, Hsin Tsung; Chen, Hui Lung; Ho, Jia-Jen.

In: Journal of Physical Organic Chemistry, Vol. 23, No. 2, 01.02.2010, p. 134-140.

Research output: Contribution to journalArticle

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AB - The reaction mechanisms as well as substituted effect and solvent effect of the enyne-allenes are investigated by Density Functional Theory (DFT) method and compared with the Myers-Saito and Schmittel reactions. The Myers-Saito reaction of non-substituted enyne-allenes is kinetically and thermodynamically favored as compared to the Schmittel reaction; while the concerted [4 + 2] cycloaddition is only 1.32 kcal/mol higher than the C 2 -C 7 cyclization and more exothermic (δ R E = -69.38 kcal/mol). For R1=CH 3 and t-Bu, the increasing barrier of the C 2 -C 7 cyclization is higher than that for the C 2 -C 6 cyclization because of the steric effect, so the increased barrier of the [4 + 2] cycloaddition is affected by such substituted electron-releasing group. Moreover, the strong steric effect of R 1 = t-Bu would shift the C 2 -C 7 cyclization to the [4 + 2] cycloaddition. On the other hand, for R 1 =Ph, NH 2 , O - , NO 2 , and CN substituents, the barrier of the C 2 -C 6 cyclization would be more diminished than the C 2 -C 7 cyclization due to strong mesomeric effect; the reaction path of C 2 -C 7 cyclization would also shift to the [4 + 2] cycloaddition. The solvation does not lead to significant changes in the potential-energy surface of the reaction except for the more polar surrounding solvent such as dimethyl sulfoxide (DMSO), or water.

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