Shibaev V N, Danilov L L
Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow.
Biochem Cell Biol. 1992 Jun;70(6):429-37. doi: 10.1139/o92-066.
Efficient methods were developed in our group in recent years for chemical synthesis of polyprenyl phosphates, polyprenyl monophosphate sugars, and polyprenyl diphosphate sugars, which were known to serve as important intermediates in biosynthesis of complex carbohydrates. A simple procedure was developed involving the phosphorylation of aliphatic alcohols with tetra-n-butylammonium dihydrogen phosphate and trichloroacetonitrile. Monophosphates of various natural and modified dolichols and polyprenols, as well as the derivatives of retinol, cholesterol, and nonacosanol, were prepared in high yields. First syntheses of dolichyl thiophosphate and dolichyl hydrogen phosphonate were developed, and these derivatives were of interest as analogs of dolichyl phosphate. Polyprenyl monophosphate sugars, including derivatives of alpha- and beta-anomers of D-glucopyranose, D-galactopyranose, D-mannopyranose, and 2-acetamido-2-deoxy-D-glucopyranose, were obtained smoothly from moraprenyl trichloroacetimidate and acylated glycosyl phosphates after deprotection. A method for the synthesis of polyprenyl diphosphate sugars from polyprenyl phosphoroimidazolidate and unprotected glycosyl phosphates was shown to be applicable for a wide range of the monosaccharide derivatives including hexoses, deoxyhexoses, 2-acetamido-2-deoxyhexoses, and uronic acids. A series of the oligosaccharide derivatives was also prepared by this method.
近年来，我们小组开发了高效的方法用于化学合成聚异戊二烯磷酸酯、聚异戊二烯单磷酸糖和聚异戊二烯二磷酸糖，这些物质被认为是复杂碳水化合物生物合成中的重要中间体。开发了一种简单的方法，该方法涉及用磷酸二氢四丁铵和三氯乙腈对脂肪醇进行磷酸化。各种天然和修饰的多萜醇和聚异戊二烯醇的单磷酸酯，以及视黄醇、胆固醇和二十九烷醇的衍生物，均以高产率制备。首次合成了硫代磷酸多萜醇酯和膦酸氢多萜醇酯，这些衍生物作为磷酸多萜醇酯的类似物备受关注。从异戊二烯基三氯乙酰亚胺酯和酰化糖基磷酸酯脱保护后顺利获得了聚异戊二烯单磷酸糖，包括D-吡喃葡萄糖、D-吡喃半乳糖、D-吡喃甘露糖和2-乙酰氨基-2-脱氧-D-吡喃葡萄糖的α-和β-异头物的衍生物。从聚异戊二烯磷酰咪唑啉酸酯和未保护的糖基磷酸酯合成聚异戊二烯二磷酸糖的方法被证明适用于广泛的单糖衍生物，包括己糖、脱氧己糖、2-乙酰氨基-2-脱氧己糖和糖醛酸。通过该方法还制备了一系列寡糖衍生物。
