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

Domingo, LR; Aurell, MJ; Perez, P.; Contreras R.

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.

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Título según WOS: Origin of the synchronicity on the transition structures of polar Diels-Alder reactions. Are these reactions [4+2] processes?
Título según SCOPUS: Origin of the synchronicity on the transition structures of polar Diels-Alder reactions. Are these reactions [4 + 2] processes?
Título de la Revista: Journal of Organic Chemistry
Volumen: 68
Número: 10
Editorial: American Chemical Society
Fecha de publicación: 2003
Página de inicio: 3884
Página final: 3890
Idioma: English
URL: http://pubs.acs.org/doi/abs/10.1021/jo020714n
DOI:

10.1021/jo020714n

Notas: ISI, SCOPUS