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

Research output: Contribution to journalArticlepeer-review

51 Citations (Scopus)

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 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.

Original languageEnglish
Pages (from-to)2120-2133
Number of pages14
JournalJournal of Organic Chemistry
Volume74
Issue number5
DOIs
Publication statusPublished - 6 Mar 2009

ASJC Scopus subject areas

  • Organic Chemistry

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