期刊
JOURNAL OF ORGANIC CHEMISTRY
卷 74, 期 5, 页码 2120-2133出版社
AMER CHEMICAL SOC
DOI: 10.1021/jo8027104
关键词
-
资金
- Spanish Government [CTQ2006-14297/BQU]
- Algerian MESRS
- Fondecyt [1060961, 1070378, 7080026]
- Universidad Andres Bello (UNAB) [DI 21-06/R, 45-08/R]
Numerous 2,5-diaryl-1,3-dioxolane-4,4-dicarbonitriles and 2,4-diphenyl-1,3-oxazoldine-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, I-naphthaldehyde, indole-3-carboxaldehyde, furan-2-carboxaldehyde, and thiophene-2-carboxaldehyde), the reactions performed with imines (N-(phenylmethylene)methanamine, N-(1,3-benzodioxol-5-ylmethylene)propylamine, N-(1,3-betizodioxol-5-ylm-ethylene)butylamine, and N-(1,3-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.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据