A Combined Experimental and Theoretical Study of the Polar [3+2] Cycloaddition of Electrophilically Activated Carbonyl Ylides with Aldehydes and Imines

Bentabed-Ababsa, G; Derdour, A; Roisnel T.; Saez, JA; Perez, P.; Chamorro, E.; Domingo, LR; Mongin, F

Abstract

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 Ar-(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. © 2009 American Chemical Society.

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Título según WOS: A Combined Experimental and Theoretical Study of the Polar [3+2] Cycloaddition of Electrophilically Activated Carbonyl Ylides with Aldehydes and Imines
Título según SCOPUS: A combined experimental and theoretical study of the polar [3 + 2] cyeloaddition of electrophilically activated carbonyl ylides with aldehydes and imines
Título de la Revista: Journal of Organic Chemistry
Volumen: 74
Número: 5
Editorial: American Chemical Society
Fecha de publicación: 2009
Página de inicio: 2120
Página final: 2133
Idioma: English
URL: http://pubs.acs.org/doi/abs/10.1021/jo8027104
DOI:

10.1021/jo8027104

Notas: ISI, SCOPUS