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

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

9 Citations (Scopus)

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 C2-C7 cyclization and more exothermic (δRE = -69.38 kcal/mol). For R1=CH3 and t-Bu, the increasing barrier of the C2-C 7 cyclization is higher than that for the C2-C6 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 R1 = t-Bu would shift the C2-C7 cyclization to the [4 + 2] cycloaddition. On the other hand, for R1 =Ph, NH2, O-, NO 2, and CN substituents, the barrier of the C2-C 6 cyclization would be more diminished than the C2-C 7 cyclization due to strong mesomeric effect; the reaction path of C2-C7 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

Keywords

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

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry

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