Pajouhesh H, Hancock A J
J Lipid Res. 1983 May;24(5):645-51.
A series of six analogs of phosphatidylserine (PS) was synthesized in which the conformational mobility of the backbone was limited. Each analog was a derivative of one of the three diastereoisomeric cyclopentane-1,2,3-triols, so that the glycerol moiety of the PS was, in effect, replaced by each cyclopentane-1,2,3-triol. Four of the members of the series were vicinal dipalmitates [1,2/3-(1P); 1,2/3-(3P); 1,2,3/0-(1P); 1,3/2-(1P)] while the other two members were "unnatural" in that they contained a 2-phosphate group. The two 2-phosphate derivatives were meso-forms and each of the other four derivatives was a DL-pair. Each PS analog was obtained as a stable microcrystalline precipitate analyzing for the monohydrate of a mixture of mono- and di-sodium salts. The infrared spectra, melting behavior, and chromatographic mobility of each sodium salt mixture resembled those obtained for bovine (glycero-)-phosphatidyl-L-serine; the stereochemical differences in the ring caused only marginal variation in these properties. The optical rotation values of the compounds varied with the stereochemistry of the ring. The all-trans-2-phosphate isomer 8d exhibited a negative rotation value, in contrast to each of the other isomers. The all-trans isomer [1,3/2-(1P)] was shown to undergo diazometholysis with diazomethane to give the dimethyl ester of cyclopentano-phosphatidic acid.
合成了一系列六种磷脂酰丝氨酸（PS）类似物，其中主链的构象流动性受到限制。每个类似物都是三种非对映异构环戊烷 - 1,2,3 - 三醇之一的衍生物，因此PS的甘油部分实际上被每种环戊烷 - 1,2,3 - 三醇所取代。该系列中的四个成员是邻位二棕榈酸酯[1,2/3-(1P); 1,2/3-(3P); 1,2,3/0-(1P); 1,3/2-(1P)]，而另外两个成员是“非天然的”，因为它们含有2 - 磷酸基团。这两种2 - 磷酸衍生物是内消旋形式，其他四种衍生物中的每一种都是DL对。每种PS类似物均以稳定的微晶沉淀形式获得，分析结果为单钠盐和二钠盐混合物的一水合物。每种钠盐混合物的红外光谱、熔化行为和色谱迁移率与牛（甘油 - ） - 磷脂酰 - L - 丝氨酸的相似；环中的立体化学差异仅导致这些性质的微小变化。这些化合物的旋光值随环的立体化学而变化。与其他异构体相比，全反式 - 2 - 磷酸异构体8d表现出负旋光值。全反式异构体[1,3/2-(1P)]经重氮甲烷进行重氮甲基化反应生成环戊烷 - 磷脂酸二甲酯。
