Origin of the synchronicity on the transition structures of polar Diels-Alder reactions. Are these reactions [4 + 2] processes?

Luis R. Domingo, M. José Aurell, Patricia Pérez, Renato Contreras

Research output: Contribution to journalArticlepeer-review

121 Citations (Scopus)

Abstract

The transition structures (TSs) for a series of related Diels-Alder reactions between cyclopentadiene and mono-, di-, tri-, and tetracyanoethylene derivatives have been studied with use of DFT methods at the B3LYP/6-31G* computational level. The increase of the electron-withdrawing substitution on ethylene increases the rate of these polar cycloadditions. However, the symmetric arrangement of cis and trans 1,2-di- and tetracyanoethylenes decreases the effectiveness of the substitution, which can be related to the symmetry found at the corresponding TSs. A DFT analysis of the global and local electrophilicity power of these series of cyano ethylenes provides a sound explanation about the nature of these synchronous processes. The present theoretical study is in agreement with the experimental outcomes.

Original languageEnglish
Pages (from-to)3884-3890
Number of pages7
JournalJournal of Organic Chemistry
Volume68
Issue number10
DOIs
Publication statusPublished - 16 May 2003

ASJC Scopus subject areas

  • Organic Chemistry

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