1986 Fiscal Year Final Research Report Summary
Synthetic Research Work of Compounds Related to Carbohydrates and Nucleic Acids
| Project/Area Number |
59430006
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| Research Category |
Grant-in-Aid for General Scientific Research (A)
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| Allocation Type | Single-year Grants |
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| Research Field |
有機化学一般
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| Research Institution | Tokyo Institute of Technology |
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Principal Investigator |
ISHIDO Yoshiharu Department of Chemistry, Faculty of Science, Tokyo Institute of Technology, 理学部, 教授 (60016037)
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| Co-Investigator(Kenkyū-buntansha) |
ARAKI Younosuke Department of Chemistry, Faculty of Science, Tokyo Institute of Technology, 理学部, 助手 (50016094)
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| Project Period (FY) |
1984 – 1986
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| Keywords | Glycosyl Fluorides / Glycosylation / Selective Protection / Oligodeoxyribonucleotides / グリコシル化 |
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| Research Abstract |
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.
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