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Synlett 2005(17): 2688-2690  
DOI: 10.1055/s-2005-917091
LETTER
© Georg Thieme Verlag Stuttgart · New York

Reactions of Vinylcyclopropane Epoxides with Samarium and Phosphorus Iodides

Alain Krief*a, Willy Dumonta, Diane Baillieula,b
a Laboratoire de Chimie Organique de Synthèse, Facultés Universitaires N.-D. de la Paix, 61 rue de Bruxelles, Namur, 5000, Belgium
b Fonds pour la Formation à la Recherche dans l’Industrie et l’Agriculture, 5 rue d’Egmont, Bruxelles 1000, Belgium
Fax: +32(81)724536; e-Mail: alain.krief@fundp.ac.be;
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Publication History

Received 17 June 2005
Publication Date:
05 October 2005 (online)

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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

    References

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3

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.

5

One 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.