- 著者
- 佐野 友春 井上 英夫 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.33, no.9, pp.3595-3598, 1985-09-25 (Released:2008-03-31)
- 参考文献数
- 15
- 被引用文献数
- 6 10
2'-Deoxy-6, 2'-methano-cyclouridine, a carbon-bridged cyclonucleoside fixed in a high-anti conformation, was synthesized. Treatment of a 3', 5'-O-protected 6-cyano-2'-O-imidazolythiocarbonyluridine with tri-n-butyltin hydride afforded a 6, 2'-oxomethano-cyclouridine derivative in low yield. Base treatment of 5-bromo-2'-deoxy-2' (S)-ethoxycarbonylmethyl-3', 5'-O-(tetraisopropyldisiloxane-1, 3-diyl) uridine resulted in an intramolecular Michael reaction followed by dehydrobromination to give the 6, 2'-cyclonucleoside. The latter was de-ethoxycarbonylated by treatment with sodium chloride and water in dimethylsulfoxide followed by desilylation to furnish the title compound.
- 著者
- 佐野 友春 周東 智 井上 英夫 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.33, no.9, pp.3617-3622, 1985-09-25 (Released:2008-03-31)
- 参考文献数
- 7
- 被引用文献数
- 25 41
The reaction of methylenetriphenylphosphorane with 2'-keto-3', 5'-O-(tetraisopropyldisiloxane-1, 3-diyl) uridine afforded the 2'-methyleneuridine (1). Oxidation of 1 with osmium tetroxide and tert-butyl hydroperoxide or N-methylmorpholine-N-oxide afforded a mixture of a 2'-hydroxymethyluridine (2) and its arabinosyl isomer. Oxidation at lower temperature gave the former as the main product. Compound 2 was converted to the 5-bromo-2'-iodomethyl derivative (3) through the 2'-mesyloxy compound, and 3 was treated with tri-n-butyltin hydride to give the 6, 2'-methano-cyclo-5, 6-dihydro derivative (4). Compound 4 was dehydrobrominated and deprotected to furnish 6, 2'-methano-cyclouridine, a uridine fixed in high-anti conformation. Some results on the synthesis and cleavage of the 2'-spiro-epoxy derivative prepared from the 2'-ketouridine are also presented.
- 著者
- 佐野 友春 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.1, pp.423-425, 1986-01-25 (Released:2008-03-31)
- 参考文献数
- 13
- 被引用文献数
- 10 11
The synthesis of 6, 3'-methanouridine was achieved by condensation of 2, 4-dimethoxy-6-lithiomethylpyrimidine with 5-O___--(tert-butyldi-methyl)silyl-1, 2-O___--isopropylidene-3-ketoxylose, followed by intramolecular glycosylation and deprotection. 6, 3'-Methanocytidine was also prepared from the 4-O___--methyl intermediate. The title compounds are the first example of uridine and cytidine fixed between C-6 and the 3'-position of pyrimidine nucleosides by a methylene group.