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On the [2,3]-sigmatropic rearrangements of sulfenate esters derived from alkenynols: synthesis of vinylallene and vinylacetylene sulfoxides.

✍ Scribed by Eugène M.G.A. van Kruchten; William H. Okamura

Publisher
Elsevier Science
Year
1982
Tongue
French
Weight
257 KB
Volume
23
Category
Article
ISSN
0040-4039

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✦ Synopsis

Suunnary: The reactions of various alkenynols with phenylsulfenyl chloride result in the formation of either vinylallene sulfoxides or vinylacetylene sulfoxides, depending on the substitution pattern of the starting material. Vinylallenesl are useful intermediates in organic synthesis, for example in the preparation of cyclopentenones2 as well as polyenes such as vitamins A (retinoids) 3 and D. 4 The vinylallene moiety is also present in certain natural products, such as the sex attractant of the male Dried Bean Beetle. 5 The development of simple new routes to usefully functionalized vinylallenes should therefore be extremely valuable. Accordingly, we have explored the feasibility of utilizing Homer's 6 allenylphenylsulfoxide synthesis for the preparation of vinylallene sulfoxides.

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✍ Philip Magnus; Cyril Ollivier 📂 Article 📅 2002 🏛 Elsevier Science 🌐 French ⚖ 404 KB

The intermediate 6 can be converted into enone 13 using a [2.3]sigmatropic sulfoxide rearrangement as the key transformation. The C-13 hydroxylation of 13 was studied, and found to give 14 (epimeric to guanacastepene A). Examination of silyl enol ethers of 13 demonstrated the ready isomerization of