The first density functional study on the [4 + 2]-cycloaddition reactions of 1,2-diaza-1,3-butadiene with alkenes

M. Avalos, R. Babiano, F. R. Clemente, P. Cintas, R. Gordillo, J. L. Jimenez, J. C. Palacios

Research output: Contribution to journalArticle

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Abstract

The hetero-Diels-Alder reactions of 1,2-diaza-1,3-butadiene with ethylene, methyl vinyl ether, and methyl acrylate have been investigated theoretically with the aid of density functional theory using the Becke3LYP/6-31G(d) computational level. In the reactions with substituted alkenes, the transition states are concerted but asynchronous; the shortest bond-forming distance involves the nonsubstituted carbon of the alkene. In agreement with the experimental results, the reaction with methyl vinyl ether proceeds with high endo stereoselectivity and with complete regioselectivity to form the 6-methoxy cycloadduct. The conformational study of the transition states shows a sharp s-trans preference. In contrast, the [4 + 2]-cycloaddition of 1,2-diaza-1,3-butadiene with methyl acrylate have been found to occur with low regio- and stereoselectivity but with a s-cis preference in the transition structures.

Original languageEnglish (US)
Pages (from-to)8251-8259
Number of pages9
JournalJournal of Organic Chemistry
Volume65
Issue number24
DOIs
StatePublished - Dec 1 2000

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Stereoselectivity
Regioselectivity
Cycloaddition
Alkenes
Propylene
Density functional theory
Carbon
vinyl ether
methyl acrylate
1,3-butadiene

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

The first density functional study on the [4 + 2]-cycloaddition reactions of 1,2-diaza-1,3-butadiene with alkenes. / Avalos, M.; Babiano, R.; Clemente, F. R.; Cintas, P.; Gordillo, R.; Jimenez, J. L.; Palacios, J. C.

In: Journal of Organic Chemistry, Vol. 65, No. 24, 01.12.2000, p. 8251-8259.

Research output: Contribution to journalArticle

Avalos, M. ; Babiano, R. ; Clemente, F. R. ; Cintas, P. ; Gordillo, R. ; Jimenez, J. L. ; Palacios, J. C. / The first density functional study on the [4 + 2]-cycloaddition reactions of 1,2-diaza-1,3-butadiene with alkenes. In: Journal of Organic Chemistry. 2000 ; Vol. 65, No. 24. pp. 8251-8259.
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