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DOI: 10.1055/s-2005-917091
Reactions of Vinylcyclopropane Epoxides with Samarium and Phosphorus Iodides
Publication History
Publication Date:
05 October 2005 (online)

Abstract
Samarium diiodide on one hand, diphosphorus tetraiodide, and phosphorus triiodide on the other, react with vinylcyclopropane epoxides to produce either allylic alcohols or vinylcyclopropanes resulting from cyclopropane ring-opening or deoxygenation of the epoxide, respectively.
Key words
deoxygenation - epoxides - olefins - radical reaction - ring-opening
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They result from the epoxidation of the corresponding vinyl cyclopropanes with m-chloro-perbenzoic acid in CH2Cl2.
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Ethyl oxido-chrysanthemate used in this work has been synthesized by epoxidation of a 83:17 mixture of trans/cis-stereoisomers of ethyl chrysanthemate (93% yield).
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References
This reaction leads, when carried out in THF in the absence of t-BuOH at 20 °C for 150 h, to the allyl alcohol 3a (7% yield, compare to Scheme [1] , entry a) or to an intractable mixture of compounds if instead performed at reflux.
5One of the referee made the following observation which is in agreament with the author view: it is paradoxal that the phenyl group, which is a better spin delocalized entity than methyl carboxyl, methyl or methoxymethyl groups, is the one which leads to the lower amount of ring-opened product.