A combined experimental and theoretical study of the polar [3 + 2] cyeloaddition of electrophilically activated carbonyl ylides with aldehydes and imines

Ghenia Bentabed-Ababsa, Aicha Derdour, Thierry Roisnel, Jose A. Sáez, Patricia Pérez, Eduardo Chamorro, Luis R. Domingo, Florence Mongin

Resultado de la investigación: Contribución a una revistaArtículorevisión exhaustiva

51 Citas (Scopus)

Resumen

Numerous 2,5-diaryl-1,3-dioxolane4,4-dicarbonitriles and 2,4-diphenyl-1,3-oxazolidine-5,5-dicarbonitriles have been synthesized by [3 + 2] cycloaddition reactions between carbonyl ylides generated from epoxides and aldehydes or imines. In contrast to the use of aldehydes (3,4,5- trimethoxybenzaldehyde, piperonal, 1-naphthaldehyde, indole-3carboxaldehyde, furan-2-carboxaldehyde, and thiophene-2-carboxaldehyde), the reactions performed with imines (/V-(pheny]methylene)methanamine, N-(1,3-benz(xlioxol-5- ylmethylene)propylamine, N-(1,3-benzodioxol-5-ylmethylene)butylamine, and Ař-(l,3-benzodioxol-5-ylmethylene)benzylamine) proceed diastereoselectively. The effect of microwave irradiation on the outcome of the reaction was studied. The mechanism of these [3 + 2] cycloaddition reactions has been theoretically investigated using DFT methods. These cycloadditions, which have one-step mechanisms, consist of the nucleophilic attack of the aldehyde oxygen or imine nitrogen on the carbonyl ylide. For the reaction with aldehydes, a back-donation effect is responsible for the unexpected reverse charge transfer found at the transition structure. The analysis of the reactivity indexes indicates that the large electrophilic character of the carbonyl ylides induces them to act as strong electrophiles in these polar [3 + 2] cycloaddition reactions.

Idioma originalInglés
Páginas (desde-hasta)2120-2133
Número de páginas14
PublicaciónJournal of Organic Chemistry
Volumen74
N.º5
DOI
EstadoPublicada - 6 mar 2009

Áreas temáticas de ASJC Scopus

  • Química orgánica

Huella

Profundice en los temas de investigación de 'A combined experimental and theoretical study of the polar [3 + 2] cyeloaddition of electrophilically activated carbonyl ylides with aldehydes and imines'. En conjunto forman una huella única.

Citar esto