Synthetic Research Work of Compounds Related to Carbohydrates and Nucleic Acids

糖基氟化物在糖基化反应中的出色应用(Mukaiyama等人)使我们开发了高效的制备方法，包括六氟丙烯与1-羟基糖衍生物的反应。氟化物与烯醇型三甲基硅醚、氰基三甲基硅烷和烯丙基三甲基硅烷在Lewis酸催化下发生偶联反应，得到相应的C-糖基化合物。在一系列反应结果的基础上，对该反应的空间化学和反应机理进行了合理化。2‘-脱氧核糖核苷以高区域选择性与芳酰氯反应高产率地得到5’-芳酸酯，5‘-芳酸酯按常规方法有效地转化为相应的2’，3‘-双脱氧核糖核苷。对于核糖核苷来说，酰化过程也是有用的，根据酰氯的量得到它们的5‘-酰化和/或2’，5‘-二酰化，后者通过Wakogel C-300处理得到3’，5‘-二酰化。在通常的方式下，它们被转化为3‘-和2’-THP衍生物，它们被认为是合成寡核苷酸的关键中间体，因此，我们进行了一系列同时具有2‘-5’和3‘-5磷酸二酯键的寡核苷酸合成，直到十一聚体。值得注意的是，一种新的聚合物载体方法与带有4-(2-羟乙基磺酰基)二氢肉桂酸酯官能化的纤维醋酸酯结合，由于其溶解性能，可以有效地执行寡核苷酸片段的偶联反应，展示了液相和固相方法的优点。此外，还开发了含有核苷的碳水化合物羟基的高区域选择性苯氨基甲酰化、甲氧甲基化和三异丙基硅基化，以及核糖核苷的核酸碱基保护。

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.