1 0 0 0 OA Synthesis of 6, 5'-Cyclo-5'-deoxyuridines by Radical Cyclization : Nucleosides and Nucleotides. L
- 著者
- 上田 享 碓井 博幸 周東 智 井上 英夫
- 出版者
- The Pharmaceutical Society of Japan
- 雑誌
- Chemical and Pharmaceutical Bulletin (ISSN:00092363)
- 巻号頁・発行日
- vol.32, no.9, pp.3410-3416, 1984-09-25 (Released:2008-03-31)
- 参考文献数
- 22
- 被引用文献数
- 18 24
6, 5'-Cyclo-5'-deoxyuridine, a fixed anti form of uridine, was synthesized by a radical cyclization of 5'-bromo (or iodo)-5'-deoxy-2', 3'-O-isopropylidene-5-chloro (or bromo)-uridine with tri-■-butyltin hydride followed by dehydrohalogenation and deacetonation. The 5-bromo and 4-thio derivatives of the cyclouridine were also prepared and were converted to the 2', 3'-cyclic phosphates. These nucleotides were hydrolyzed by pancreatic ribonuclease. The result showed that the enzyme recognizes the pyrimidine nucleotides in the anti form. 6, 5'-Cyclo-5'-deoxycytidine was also synthesized by two routes.
- 著者
- 碓井 博幸 上田 亨
- 出版者
- The Pharmaceutical Society of Japan
- 雑誌
- Chemical and Pharmaceutical Bulletin (ISSN:00092363)
- 巻号頁・発行日
- vol.34, no.4, pp.1518-1523, 1986-04-25 (Released:2008-03-31)
- 参考文献数
- 10
- 被引用文献数
- 12 16
Treatment of 3', 5'-O-(tetraisopropyldisiloxane-1, 3-diyl)-2'-ketoadenosine (1) with methylenetriphenylphosphorane gave the 2'-methylene derivative (2). Hydroxylation of 1 with OsO4 gave the 2'-hydroxymethyladenosine (4), which was then converted to the 2'-phenylthiomethyl derivative (5). Photocyclization followed by deprotection of the product furnished 8, 2'-methanoadenosine (7), and adenosine fixed in a high-anti conformation. Oxidation of a 2'-hydroxyethylideneadenosine with OsO4 gave the 2'-dihydroxyethyladenosine (10), which was also converted to the 2'-(2-phenylthioethyl) derivative (11). The photocyclization of 11 and successive elimination of the hydroxyl group gave the 8, 2'-ethenoadenosine (13). Catalytic hydrogenation and deprotection of 13 afforded 8, 2'-ethanoadenosine (15). The circular dichroism spectral features of C-cycloadenosine are discussed.
- 著者
- 碓井 博幸 松田 彰 上田 亨
- 出版者
- The Pharmaceutical Society of Japan
- 雑誌
- Chemical and Pharmaceutical Bulletin (ISSN:00092363)
- 巻号頁・発行日
- vol.34, no.5, pp.1961-1967, 1986-05-25 (Released:2008-03-31)
- 参考文献数
- 12
- 被引用文献数
- 5 7
Guanosine fixed in the high-anti conformation by means of an 8, 2'-methylene bridge was prepared. N2-Acetyl-O6-ethylguanosine (2) was converted to the 3', 5'-O-(tetraisopropyldisiloxane-1, 3-diyl) derivative (3). Oxidation of 3 to the 2'-keto derivative (4) and successive coupling with methylenetriphenylphosphorane gave the 2'-methylidene derivative (5) and its α-anomer. The 2'-methylidene function of 5 was hydroxylated, and the 2'-hydroxymethyl group was modified to give the phenylthiomethyl derivative (6). Photocyclization of 6 followed by deprotection of the sugar and base protecting groups furnished 8, 2'-methanoguanosine (12). The alpha anomer of 12 was likewise prepared. The circular dichroism spectra of 12, its α-anomer, and related compounds were measured.