Synthetic Study of Biologically Related Compounds Using Cellulose Derivatives as a Polymer-support

1.寡核苷酸的合成研究：(1)醋酸酯纤维素衍生物可用于合成DNA型8-聚体和RNA型13-聚体。(2)针对假性尿苷(Psi)、1-β-D-呋喃核糖胸腺嘧啶(RT)、5，6-二氢尿苷(D)和磷酸盐等官能团的有效保护方法的发展，我们成功地合成了RNA型12-聚体(psi和RT)、11-聚体(5‘-末端磷酸盐通过聚合物载体)和8-聚体(通过CPG-支持)。2.2’-Omicron-(α-和β-D-核呋喃糖基)腺苷的合成研究：α-异构体，被称为聚(阿糖苷-呋喃)的关键化合物β-异构体，位于酵母启动子tRNA^&lt的第64位；通过腺苷2‘-羟基衍生物与D-呋喃核糖衍生物的酸催化偶联反应，以较高的立体选择性合成了MET和GT；。3.低聚糖的合成研究：通过糖基受体与含1-苯氧基碳酸酯和1-苯基氨基甲酸酯的糖基供体的酸催化偶联反应，开发了糖基化反应的新方法。4.稳定同位素标记核苷的合成研究：实现了(2‘R)-和(2’-S)-[2‘-^2H]-2’-脱氧核糖核苷的高度非对映选择性合成，以及合成含外环氨基的核苷的有效方法。这些产物主要用于核酸-核酸或核酸-蛋白质等精细构象相互作用的核磁共振谱研究。

1.Synthetic Study of Oligonucleotides : (1)The cellulose acetate derivatives were found to be feasible for the syntheses of DNA-type8-mer and of RNA-type 13-mer. (2)Development of efficient methods for the protection of functional groups involved in pseudouridine (psi), 1-beta-D-ribofuranosylthymine(rT), 5, 6-dihydrouridine(D), and phosphate, led us to successful syntheses of RNA-type 12-mer involving psi and rT, 11-mer involving 5'-terminal phosphate through the polymer-support, and 8-mer involving D through the CPG-support.2.Synthetic Study of 2'-omicron-(alpha- and beta-D-ribofuranosyl)adenosines : The alpha-isomer, known as the key compound of poly(ADP-ribose), and the beta-isomer, found as the corresponding 5'-phosphate located at 64th position of Yeast initiator tRNA^<Met>, were synthesized with high stereoselectivity by the acid-catalyzed coupling reaction of an adenosine 2'-hydroxyl derivative with D-ribofuranosyl derivatives functionalized at their anomeric position.3.Synthetic Study of Oligosaccharides : Novel approaches to glycosylation in terms of acid-catalyzed coupling reaction of a glycosyl acceptor with glycosyl donors bearing 1-phenoxylcarbonate and 1-phenylcarbamate were developed. and the latter was found to be particularly feasible for the synthesis of oligosaccharides such as Le^Y antigenic tetrasaccharide.4.Synthetic Study of Nucleosides Specifically Labeled with Stable Isotopes : Highly diastereoselective syntheses of (2'R)- and (2'S)-[2'-^2H]-2'-deoxyribonucleosides, and efficient method for the syntheses of nucleosides bearing exocyclic amino groups, were labeled with ^<15>N atom, were realized. These products essentially contribute to the NMR spectroscopic study on delicate conformational analysis on interactions of nucleic acid-nucleic acid or nucleic acid-protein etc.