- Synthesis of new trans double-bond sphingolipid analogues: Δ4,6 and Δ6 ceramides
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Unsaturation was introduced at Δ4,6 and Δ6 of the sphingoid chain of naturally occurring ceramide 1 via a β-keto sulfoxide (12) and sulfone (18) derived from N-Boc-L-serine methyl ester acetonide (9), affording two novel ceramide analogues, (2S,3R)-2-octanoylamidooctadeca-(4E,6E)-diene-1,3diol (2) and (2S,3R)-2-octanoylamidooctadec-(6E)-ene-1,3-diol (3). After C-alkylation of 12 with (E)1-bromo-2-tetradecene (8), a trans double bond was installed by elimination of PhS(O)H, providing conjugated dienone oxazolidine 13. Reaction of 18 with 8, followed by desulfonation (Al(Hg)), afforded keto-oxazolidine 20, which bears a (E)-Δ6 double bond. The syntheses of analogues 2 and 3 from ketones 13 and 20, respectively, were completed by the following sequence of reactions: diastereoselective reduction (NaBH4/CeCl3 or DIBAL-H), hydrolysis of the oxazolidine ring, liberation of the amino group, and installation of the N-amide group.
- Chun, Jiong,Li, Guoqing,Byun, Hoe-Sup,Bittman, Robert
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- A concise route to D-erythro-sphingosine from N-Boc-L-serine derivatives via sulfoxide or sulfone intermediates
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Sulfoxide and sulfone intermediates 7 and 15, respectively, were employed to synthesize synthons 3 and 4, which are readily converted to the naturally occurring (2S,3R,4(E))-sphingosine 1 and (2S,3R)-sphinganine 2.
- Chun, Jiong,Li, Guoqing,Byun, Hoe-Sup,Bittman, Robert
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p. 375 - 377
(2007/10/03)
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