3',5'-diacetyl-3-methyl-2'-deoxythymidine | 144874-49-7

• 分子结构分类: 有机化合物 - 核苷、核苷酸和类似物 - 嘧啶核苷
• 英文名称: 3',5'-diacetyl-3-methyl-2'-deoxythymidine
• 英文别名: 3',5'-di-O-acetyl-3-methylthymidine；3',5'-di-O-acetyl-N³-methylthymidine；3-Methyl-thymidin-3',5'-diacetat；O^3'_,O5'-diacetyl-3-methyl-thymidine；[(2R,3S,5R)-3-acetyloxy-5-(3,5-dimethyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methyl acetate
• CAS: 144874-49-7
• 化学式: C₁₅H₂₀N₂O₇
• 分子量: 340.333
• InChiKey: NTARYRJJLKYERJ-YNEHKIRRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.2
• 重原子数：
  24
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  102
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  3',5'-diacetyl-3-methyl-2'-deoxythymidine 在 tetraphosphorus decasulfide 、 三乙胺 作用下， 以 1,4-二氧六环 、 甲醇 、 水 为溶剂， 反应 6.5h， 生成 N-3-methyl-4-thiothymidine
  参考文献：
  名称：

  Clivio, Pascale; Fourrey, Jean-Louis; Gasche, Jeanette, Journal of the Chemical Society. Perkin transactions I, 1992, # 18, p. 2383 - 2388

  摘要：

  DOI：
• 作为产物：
  描述：

  重氮甲烷 、 3,5-双-O-乙酰胸苷 以 甲醇 、 乙醚 为溶剂， 反应 14.0h， 以91%的产率得到3',5'-diacetyl-3-methyl-2'-deoxythymidine
  参考文献：
  名称：

  Oxidation of Acetylated Guanosine by 3,3-Disubstituted 1,2-Dioxetanes through Nucleophilic Attack on the Peroxide Bond: Model Studies on the Oxidative DNA Damage by Reactive Peroxides

  摘要：

  The reaction of the disubstituted 3-(methoxymethyl)-3-phenyl-1,2-dioxetane (1a) with the acetylated guanine nucleoside (2) in methanol affords 8-methoxyguanosine 5 as oxidation product, as well as guanine (6) and 1-methoxyribose 7 by deglycosylation (total yield ca. 30%). The dioxetane-derived reduction product constitutes the 1,2-diol 40, while the major dioxetane-derived product (85%) is omega-methoxyacetophenone (3a). A Grob-type fragmentation is made responsible for the exclusive formation of the dioxetane cleavage products in the reactions with the acetylated nucleosides 8-10 derived from adenine, cytosine, and thymine. Rather than redox chemistry, this guanosine oxidation, unprecedented for peroxides, is proposed to involve nucleophilic attack by the N-7 atom of the nucleosides on the peroxide bond of the dioxetane la electrophile to generate a zwitterionic intermediate. S(N)2 attack by methanol at the C-8 position of the guanine moiety in the zwitterionic intermediate leads to the 8-methoxyguanosine 5 and the diol 4a. Alternatively, heterolytic cleavage of the glycosidic bond affords the methoxylated ribose 7 (after methanol trapping) and the N-7-alkoxylated guanine. The latter, after protonation, subsequently undergoes Grob fragmentation into guanine (6) and the dioxetane decomposition products omega-methoxyacetophenone (3a) and formaldehyde. We propose that the present novel oxidation of guanosine is general for electrophilic peroxides and may constitute a prominent route of oxidative DNA damage. In contrast, the corresponding 3-(bromethyl)-3-phenyl- 1,2-dioxetane (1b) gave with the guanosine 2 an intractable, complex product mixture, for which presumably the bromo substituent is responsible on account of competitive alkylation chemistry. However, with the 2'-deoxythymidine 10, a novel acid-catalyzed ring-opening of the bromo-substituted dioxetane Ib to its beta-methoxy hydroperoxide 11b is observed, a reaction which does not take place for the methoxy-substituted dioxetane 1a. This unusual process for simple dioxetanes is rationalized in terms of stabilization of the intermediary benzylic cation by the adjacent beta-bromo substituent through neighboring group participation.

  DOI：

  10.1021/ja00115a002

文献信息

• Ueda; Miyawaki; Sugane, Pharmazie, 2000, vol. 55, # 3, p. 192 - 195
  作者：Ueda、Miyawaki、Sugane、Sakurai、Wada、Futai

  DOI：——

  日期：——