Synthesis 1993; 1993(4): 399-405
DOI: 10.1055/s-1993-25872
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Cohalogenation of Alkenes in Ethylene Oxide: Efficient Methodology for the Preparation of Allyl Vinyl Ether Precursors of γ,δ-Unsaturated Aldehydes

Jean-Pierre Dulcère* , Jean Rodriguez
  • *Laboratoire de Synthèse Organique, SM3B URA 1411, Université d' Aix-Marseille III, Faculté des Sciences de St Jérôme-D 12, Avenue Escadrille Normandie-Niemen, F-13397 Marseille Cedex 13, France
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Publication History

Publication Date:
17 September 2002 (online)

An investigation of the cohalogenation-dehydrohalogenation sequence as a method for the preparation of allyl vinyl ethers from simple olefins has been performed. Alkenes 1a-k react with bromine or chlorine in the presence of ethylene oxide at - 80°C to form β,β′-dihalo ethers 2a-k regio- and stereoselectively in high yields. Two of these β,β′-dihalo ether intermediates were selectively monodehydrohalogenated by potassium tert-butoxide to give 2-haloalkyl vinyl ethers in almost quantitative yields. Use of an excess of base produces allyl vinyl ethers 3a-k in good yields. Thermal rearrangement of the latter converts them into the corresponding γ,δ- unsaturated aldehydes 4a-j.