The Role of Asynchronous Bond Formation in the Diastereoselective Epoxidation of Cyclic Enol Ethers:  A Density Functional Theory Study

Density functional theory (DFT) (Becke3LYP functional and the D95** basis set) was used to study the influence of substitution on the dimethyldioxirane epoxidation reaction of six- and seven-membered cyclic enol ethers. In agreement with our previously reported experimental results, the calculations...

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Bibliographic Details
Published in:Journal of organic chemistry 2006-07, Vol.71 (15), p.5565-5573
Main Authors: Orendt, Anita M, Roberts, Scott W, Rainier, Jon D
Format: Article
Language:English
Subjects:
Chemistry
Cyclization
Epoxy Compounds - chemical synthesis
Epoxy Compounds - chemistry
Ethers, Cyclic - chemical synthesis
Ethers, Cyclic - chemistry
Exact sciences and technology
Models, Chemical
Models, Molecular
Molecular Structure
Organic chemistry
Oxepins - chemical synthesis
Oxepins - chemistry
Pyrans - chemical synthesis
Pyrans - chemistry
Stereoisomerism
Thermodynamics
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Summary:Density functional theory (DFT) (Becke3LYP functional and the D95** basis set) was used to study the influence of substitution on the dimethyldioxirane epoxidation reaction of six- and seven-membered cyclic enol ethers. In agreement with our previously reported experimental results, the calculations predict that substitution on the cyclic enol ether influences the level of diastereoselectivity. Apparent only from the calculations is that the degree of synchronicity in the transition state is important in the diastereoselectivity.
ISSN:0022-3263
1520-6904
DOI:10.1021/jo060502g