[2,3] Sigmatropic Rearrangement of Ethyl 2-(Diethoxyphosphoryloxy) Allyl Sulfoxides and Selenoxides. Synthetic Applications |
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| Authors: | Aleksandra Skowrońska Marek Koprowski Mary McPartlin Nick Choi |
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| Institution: | 1. Centre of Molecular and Macromolecular Studies Polish Academy of Sciences , 90-363 ?ód?, Sienkiewicza , 112 , Poland;2. School of Applied Chemistry University of North London , Holloway, London , N7 8DB , U.K. |
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| Abstract: | Abstract We have previously described regio- and stereospecific synthesis of ally1 selenides I and ally1 sulfides 2 1]. We now report on the application of 1 and 2 as attractive precursors of new, functionalized: allylic alcohols 3, α-hydroxy ketones 4 and I, 3-dienes 5. 1 and 2 are transformed by oxidation into corresponding ally1 selenoxide and sulfoxide, which display stereospecific 2,3] sigmatropic rearrangement providing after hydrolysis the allylic alcohols 3. Trans configuration of 3 was established by X-ray analysis. In some cases the rearrangement is accompanied by elimination giving the 1,3-dienes 5. Compounds 3 and 5 can be easily separated by column chromatography Dephosphorylation of 3 afforded the α-hydroxy ketones 4. |
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