A Combined Experimental and Theoretical Study of the Polar [3 + 2] Cycloaddition of Electrophilically Activated Carbonyl Ylides with Aldehydes and Imines
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http://dx.doi.org/ 10.1021/jo8027104 |
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Title
A Combined Experimental and Theoretical Study of the Polar [3 + 2] Cycloaddition of Electrophilically Activated Carbonyl Ylides with Aldehydes and IminesAuthor (s)
Date
2009Publisher
American Chemical SocietyISSN
0022-3263Type
info:eu-repo/semantics/articlePublisher version
http://pubs.acs.org/doi/abs/10.1021/jo8027104Abstract
Numerous 2,5-diaryl-1,3-dioxolane-4,4-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 ... [+]
Numerous 2,5-diaryl-1,3-dioxolane-4,4-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-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-benzodioxol-5-ylmethylene)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. [-]
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Journal of Organic Chemistry, 74, 5, p. 2120–2133Rights
Copyright © 2009 American Chemical Society
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