Synthetic Research Work of Compounds Related to Carbohydrates and Nucleic Acids

由于糖基氟化物在糖基化反应中的优异应用（Mukaiyama等），我们开发了六氟丙烯- <NHR_2>与1-OH糖衍生物反应的高效制备方法。Lewis酸催化氟化物与烯醇三甲基硅醚、氰三甲基硅烷和烯丙基三甲基硅烷的偶联反应可有效地生成相应的C -糖基化合物。根据一系列反应的结果，对反应的立体化学和机理进行了理顺。2′-脱氧核糖核苷在芳酰氯的稀释-逐滴加成过程中具有高的区域选择性得到5′-环烯酸酯，5′-环烯酸酯以通常的方式有效地转化为相应的2′，3′-二脱氧核糖核苷。酰基化过程也适用于核糖核苷根据酰基氯化物的数量生成5'-酰基化和/或2',5'-二酰基化，后者通过Wakogel C-300处理得到3',5'-二酰基化。以通常的方式，它们被转化为3‘和2’- thp衍生物，这些衍生物被称为合成低核苷酸的关键中间体，因此，我们进行了一系列具有2‘-5’和3'-5磷酸二酯键的低核苷酸合成。值得注意的是，用4-（2-羟乙基磺酰基）二氢肉桂酸功能化的醋酸纤维素作为聚合物载体，由于其溶解度的特性，可以有效地进行寡核苷酸片段的偶联反应，这表明了液相和固相方法的优越性。此外，还研究了涉及核苷的碳水化合物羟基的高区域选择性苯基氨基化、甲氧基甲基化和三异丙基硅基化，以及核糖核苷核酸碱基部分的保护。

The excellent utility of glycosyl fluorides in glycosylation reaction (Mukaiyama et al.) led us to develop their efficient preparative methods involving reaction of hexafluoropropene - <NHR_2> with 1-OH sugar derivatives. Lewis acid-catalyzed coupling reactions of the fluorides with an enol trimethylsilyl ether, cyanotrimethylsilane, and allyltrimethylsilane were effectively induced to give the corresponding C -glycosyl compounds. Based on the results obtained by a series of reactions, steresochemistry and mechanism of the reaction were rationalized.2'-Deoxyribonucleosides were aroylated with high regioselectivity to give their 5'-aroates in a high yield on treatment with an aroyl chloride through dilution - drop-by-drop - addition procedure, The 5'-aroates were efficiently converted into the corresponding 2',3'-dideoxyribonucleosides in a usual manner. The acylation procedure was also useful for ribonucleosides to give their 5'-acylates and/or 2',5'-diacylates depending on the amount of the acyl chlorides, and the latter were derived into 3',5'-diacylates by treating with Wakogel C-300. In a usual manner, they were converted to 3'- and 2'-THP derivatives which have been known as the key-intermediates for the synthesis of oligoribonucleotides, and, thus, we conducted a series of oligoribonucleotide syntheses bearing both 2'-5' and 3'-5 phosphodiester linkages up to an undecamer, It is noteworthy that a novel polymer support approach with a cellulose acetate which is functionalized with 4-(2-hydroxyethylsulfonyl)dihydrocinnamate made up possible to perform coupling reactions of oligonucleotide-fragments efficiently due to its properties in solubility, demonstrating the excellence of both liquid- and solid-phase approaches. In addition, highly regioselective phenylcarbamoylation, methoxymethylation, and triisopropylsilylation of hydroxyl groups of carbohydrates involving nucleosides, and protection of nucleic acid base moieties of ribonucleosides were developed.