| 摘要 |
PURPOSE: Provided are the methods of preparing sphingosine and sphingenine derivatives in short reaction hours. The method is highly stereospecific, and enables the synthesis of optically and sterically pure isomers. CONSTITUTION: Sphingosine and sphingenine derivatives are independently represented by the chemical formula 6 and 8, and chemical formula 9, 10 while where R1 is hydrogen or one of the low alkyl groups selected from methyl, ethyl, propyl, isopropyl, butyl, t-butyl and phenyl group, R2 is hydrogen or one of the hydroxyl protectants selected from methoxymethyl, methoxythiomethyl, triethylsilyl, triisopropylsilyl, t-butyldiphenylsilyl, t-butylmethylsilyl, trimethylsilyl, triphenylsilyl, benzyl, p-methoxybenzyl, t-butoxymethyl, tetrahydropyrazyl, 3,4-dimethoxybenzyl, o-nitrobenzyl, diphenylmethyl and triphenylmethyl group, R3 is hydrogen or one of the amine protectants selected from triphenylmethyl, allyl, di(4-methoxyphenyl)methyl, N-5-dibenzosuberyl, (4-methoxyphenyl)diphenylphenyl and 9-phenylfluororenyl group, R6 is hydrogen or C1-C30 hydrocarbon and where R7 is an acid which forms salt with amine, selected from acetic acid, formic acid, tartaric acid, methylsulfonic acid, trifluoroacetic acid, p-tosyl acid, HCl, H2SO4 and H3PO4. The synthetic scheme includes: reacting chemical formula 1 compound with CH3PO(OR5)2, to obtain the chemical formula 3 compound, where R5 is one of the groups selected from methyl, ethyl, propyl, isopropyl, butyl isobutyl, t-butyl, phenyl and benzyl group; obtaining the compound represented by chemical formula 5 by reacting the chemical formula 3 compound with R6CHO, with addition of LiCl to accelerate the reaction, where R6 is the group mentioned above; reducing ketone group of the chemical formula 5 and 7 with a catalyst selected from NaBH4, LiBH4, LiAlH4, L-selectride, diisopropyl aluminum hydride, Zn(BH4)2, Me4BH(OAc)3, NaBH3CN, LiBHEt3, LiAl(OMe)3, CeCl3·7H2O, CeCl3, SmCl3, CaCl2, ZnCl2, TiCl4, SnCl4 and MnCl2 to make sphingosine derivatives shown by chemical formula 6 or 8, and finally reducing their double bonds to make sphingenine derivatives shown by chemical formula 9 or 10 with a metal catalyst selected from Ni, Pt, Pd and Rh.
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