6,3'-methanouridine | 103931-51-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶并嘧啶类
• 英文名称: 6,3'-methanouridine
• 英文别名: (1R,9S,10R,12R)-9,12-dihydroxy-10-(hydroxymethyl)-11-oxa-2,4-diazatricyclo[7.2.1.02,7]dodec-6-ene-3,5-dione
• CAS: 103931-51-7
• 化学式: C₁₀H₁₂N₂O₆
• 分子量: 256.215
• InChiKey: CYRWFBIZSASJDA-AMCGLFBUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -2.4
• 重原子数：
  18
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  119
• 氢给体数：
  4
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  6,3'-methanouridine 在 吡啶 、 4-二甲氨基吡啶 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 5.42h， 生成
  参考文献：
  名称：

  Effect of Ribose Conformation on RNA Cleavage via Internal Transesterification

  摘要：

  RNA cleavage via internal transesterification is a fundamental reaction involved in RNA processing and metabolism, and the regulation thereof. Herein, the influence of ribose conformation on this reaction was investigated with conformationally constrained ribonucleotides. RNA cleavage rates were found to decrease in the order South-constrained ribonucleotide > native ribonucleotide >> North-constrained counterpart, indicating that the ribose conformation plays an important role in modulating RNA cleavage via internal transesterification.

  DOI：

  10.1021/jacs.8b06313
• 作为产物：
  描述：

  1,2-O-isopropylidene-5-O-(tert-butyl)dimethylsilyl-α-D-xylofuranoside 在 吡啶 、 chromium(VI) oxide 、 sodium hydroxide 、 正丁基锂 、 四丁基氟化铵 、 乙酸酐 、 四氯化锡 、 三乙胺 、 三氟乙酸 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 二氯甲烷 、 乙腈 为溶剂， 反应 10.5h， 生成 6,3'-methanouridine
  参考文献：
  名称：

  Synthesis of 6,3'-methanocytidine,6,3'-methanouridine, and their 2'-deoxyribonucleosides (nucleosides and nucleotides. LXXVII).

  摘要：

  5-O-叔丁基二甲基硅基-1，2-O-异亚丙基-α-D-赤式-3-戊基呋喃糖（4）与 2，4-二甲氧基嘧啶-6-基甲基锂（5）缩合，得到 3-嘧啶基甲基核糖衍生物（6）。改变 6 的保护基团，得到 5-O-苯甲酰基-1，2-二-O-乙酰基衍生物（8）。用氯化锡处理 8 分子内糖基化，得到 6，3'-甲醇-O4-甲基尿苷衍生物（9），进一步转化为 6，3'-甲尿苷（10）和 6，3'-甲胞苷（11）。通过 2'-咪唑基硫代羰基衍生物对 9 进行 2'-脱氧反应，经适当衍生化后，得到 2'-脱氧-6，3'-甲氰胞苷 (16) 和尿苷 (17)。

  DOI：

  10.1248/cpb.36.162

文献信息

• Nucleosides and nucleotides. LXVIII. A facile synthesis of 6,3'-methano-uridine and -cytidine from a 3-ketosugar.
  作者：Tomoharu Sano、Tohru Ueda

  DOI：10.1248/cpb.34.423

  日期：——

  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.

  通过 2，4-二甲氧基-6-硫代甲基嘧啶与 5-O____-（叔丁基二甲基）硅-1，2-O____-异亚丙基-3-酮氧基lose 缩合，然后进行分子内糖基化和脱保护，合成了 6，3'-甲氰尿苷。6，3'-甲氰胞苷也是由 4-O___-甲基中间体制备的。标题化合物是尿苷和胞苷通过亚甲基固定在嘧啶核苷的 C-6 和 3'- 位之间的第一个实例。
• YOSHIMURA, YUICHI;SANO, TOMOHARU;MATSUDA, AKIRA;UEDA, TOHRU, CHEM. AND PHARM. BULL., 36,(1988) N 1, 162-167
  作者：YOSHIMURA, YUICHI、SANO, TOMOHARU、MATSUDA, AKIRA、UEDA, TOHRU

  DOI：——

  日期：——
• Effect of Ribose Conformation on RNA Cleavage via Internal Transesterification
  作者：Fengmin Guo、Zekun Yue、Marko Trajkovski、Xiaoping Zhou、Dong Cao、Qiang Li、Baifan Wang、Xin Wen、Janez Plavec、Qian Peng、Zhen Xi、Chuanzheng Zhou

  DOI：10.1021/jacs.8b06313

  日期：2018.9.26

  RNA cleavage via internal transesterification is a fundamental reaction involved in RNA processing and metabolism, and the regulation thereof. Herein, the influence of ribose conformation on this reaction was investigated with conformationally constrained ribonucleotides. RNA cleavage rates were found to decrease in the order South-constrained ribonucleotide > native ribonucleotide >> North-constrained counterpart, indicating that the ribose conformation plays an important role in modulating RNA cleavage via internal transesterification.
• Synthesis of 6,3'-methanocytidine,6,3'-methanouridine, and their 2'-deoxyribonucleosides (nucleosides and nucleotides. LXXVII).
  作者：YUICHI YOSHIMURA、TOMOHARU SANO、AKIRA MATSUDA、TOHRU UEDA

  DOI：10.1248/cpb.36.162

  日期：——

  Condensation of 5-O-tert-butyldimethylsilyl-1, 2-O-isopropylidene-α-D-erythro-3-pentulo-furanose (4) with 2, 4-dimethoxypyrimidin-6-ylmethyllithium (5) afforded a 3-pyrimidinylmethyl-ribose derivative (6). The protecting groups of 6 were changed to give the 5-O-benzoyl-1, 2-di-O-acetyl derivative (8). The intramolecular glycosylation of 8 by treatment with stannic chloride furnished the 6, 3'-methanol-O4-methyluridine derivative (9), which was further converted to 6, 3'-methanouridine (10) and 6, 3'-methanocytidine (11). The 2'-deoxygenation of 9 by way of the 2'-imidazolylthiocarbonyl dericative gave, after appropriate derivatization, 2'-deoxy-6, 3'-methanocytidine (16) and -uridine (17).

  5-O-叔丁基二甲基硅基-1，2-O-异亚丙基-α-D-赤式-3-戊基呋喃糖（4）与 2，4-二甲氧基嘧啶-6-基甲基锂（5）缩合，得到 3-嘧啶基甲基核糖衍生物（6）。改变 6 的保护基团，得到 5-O-苯甲酰基-1，2-二-O-乙酰基衍生物（8）。用氯化锡处理 8 分子内糖基化，得到 6，3'-甲醇-O4-甲基尿苷衍生物（9），进一步转化为 6，3'-甲尿苷（10）和 6，3'-甲胞苷（11）。通过 2'-咪唑基硫代羰基衍生物对 9 进行 2'-脱氧反应，经适当衍生化后，得到 2'-脱氧-6，3'-甲氰胞苷 (16) 和尿苷 (17)。