Total synthesis of stereospecific sphingosine and ceramide
| Autor: | Y Shoyama, Dr, H Okabe, Dr, Y Kishimoto, Dr, C Costello, Dr |
|---|---|
| Jazyk: | angličtina |
| Rok vydání: | 1978 |
| Předmět: |
Resolution of ethyl D- and L-erythro-2- acetamino-3-[L(+)-acetylmandeloyloxy]-4t-octadecenoate
resolution of D- and L-erythro-2-lignoceroylamino-3-[L(+)-acetylmandeloyloxy]-4t-octadecenoate [1-3H]sphingosine N-acyl [1-3H]sphingosine doubly labeled ceramide NaBH4 reduction of ethyl 2-acylamino-3-hydroxy-4t-octadecenoate Biochemistry QD415-436 |
| Zdroj: | Journal of Lipid Research, Vol 19, Iss 2, Pp 250-259 (1978) |
| Druh dokumentu: | article |
| ISSN: | 0022-2275 |
| DOI: | 10.1016/S0022-2275(20)41565-2 |
| Popis: | A small-scale synthesis of the four sphingosine stereoisomers (D-erythro, L-erythro, D-threo, and L-threo) and lignoceroyl D- and L-erythro-sphingosines, which is suitable for synthesis of tritium-labeled compounds, is described. Ethyl DL-erythro-2-acetamino-3-hydroxy-4t-octadecenoate was esterified with L(+)-acetylmandeloyl chloride and the two diastereomers obtained were separated from each other by thin-layer or column chromatography. Each diastereomer was subjected to ethanolysis to obtain ethyl D- or L-erythro-2-amino-3-hydroxy-4t-octadecenoate which was then reduced with LiAlH4 or NaBH4 to yield D- or L-erythro-sphingosine. D-erythro-[1-3H]Sphingosine with high specific activity was prepared by using LiAl3H4 in the last step. D- and L-threo-sphingosines were synthesized from ethyl DL-threo-2-acetamino-3-hydroxy-4t-octadecenoate by using a similar procedure.Ceramide (lignoceroyl sphingosine) was prepared either by acylating sphingosine or by the following new method. Ethyl DL-erythro-2-amino-3-hydroxy-4t-octadecenoate was converted to the N-lignoceroyl derivative and esterified with L(+)-acetylmandeloyl chloride. The two diastereomers obtained were separated and each isomer was treated with a catalytic amount of sodium ethoxide. One of the products, ethyl D-erythro-2-lignoceroylamino-3-hydroxy-4t-octadecenoate, was reduced with NaBH4 to yield ceramide. N-palmitoyl DL-erythro-sphingosine was also prepared using an identical procedure. N-lignoceroyl D-erythro-[1-3H]sphingosine was prepared by NaB3H4 reduction of the corresponding amide ester. A doubly labeled ceramide, [1-14C]lignoceroyl [1-3H]sphingosine, containing high specific activity, was prepared by mixing the above N-lignoceroyl D-erythro-[1-3H]sphingosine and N-[1-14C]lignoceroyl D-erythro-sphingosine. The conversion of the doubly labeled ceramide to 3-keto derivative is also described. |
| Databáze: | Directory of Open Access Journals |
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