Orr G A, Brewer C F, Heney G
Biochemistry. 1982 Jun 22;21(13):3202-6. doi: 10.1021/bi00256a026.
A convenient three-step synthesis of the phosphorothioate analogue of phosphatidylethanolamine is described. The reaction pathway involves the conversion of a 1,2-diacyl-sn-glycerol to its corresponding thiophosphoric acid dichloride by using PSCl3 in the presence of a tertiary base. Treatment of the dichloride with ethanolamine results in the formation of a cyclic thiophosphoramidate which, upon acidification, undergoes P--N cleavage, giving rise to 1,2-diacyl-sn-glycero-3-thiophosphorylethanolamine. 31P NMR reveals that both diastereoisomers are present in equivalent amounts. It is not possible, however, to separate the two isomers by high-pressure liquid chromatography. 31P NMR amd high-pressure liquid chromatography are used to show that phospholipases A2 and C exhibit absolute and opposite stereoselectivity in the hydrolysis of the pair of diastereoisomers.
本文描述了一种便捷的三步合成磷脂酰乙醇胺硫代磷酸酯类似物的方法。反应途径包括在叔碱存在下，使用PSCl3将1,2-二酰基-sn-甘油转化为其相应的硫代磷酸二氯。用乙醇胺处理二氯化合物会形成环状硫代磷酰胺，酸化后，该环状硫代磷酰胺会发生P-N键断裂，生成1,2-二酰基-sn-甘油-3-硫代磷酰乙醇胺。31P NMR显示两种非对映异构体的含量相等。然而，通过高压液相色谱法无法分离这两种异构体。31P NMR和高压液相色谱法用于表明磷脂酶A2和C在水解这对非对映异构体时表现出绝对相反的立体选择性。
