4'-C-allyl-N⁴,O^5'-diacetyl-2',3'-didehydro-2',3'-dideoxycytidine | 174275-93-5

• 分子结构分类: 有机化合物 - 核苷、核苷酸和类似物 - 核苷和核苷酸类似物
• 英文名称: 4'-C-allyl-N⁴,O^5'-diacetyl-2',3'-didehydro-2',3'-dideoxycytidine
• 英文别名: [(2R,5S)-2-(4-acetamido-2-oxopyrimidin-1-yl)-5-prop-2-enyl-2H-furan-5-yl]methyl acetate
• CAS: 174275-93-5
• 化学式: C₁₆H₁₉N₃O₅
• 分子量: 333.344
• InChiKey: VIDWXCRISSGOHD-ZBFHGGJFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  24
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  97.3
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  4'-C-allyl-N⁴,O^5'-diacetyl-2',3'-didehydro-2',3'-dideoxycytidine 在 吡啶 、 氨 作用下， 以 甲醇 为溶剂， 生成 4'-C-allyl-5'-O-(tert-butyldiphenylsilyl)-2',3'-didehydro-2',3'-dideoxycytidine
  参考文献：
  名称：

  Allylic Substitution of 3‘,4‘-Unsaturated Nucleosides:  Organosilicon-Based Stereoselective Access to 4‘-C-Branched 2‘,3‘-Didehydro-2‘,3‘-dideoxyribonucleosides

  摘要：

  Reactions of organosilicon reagents (such as allyltrimethylsilane, silyl enol ethers, cyanotrimethylsilane) with 3',4'-unsaturated nucleosides (of uracil, N-4-acetylcytosine, and hypoxanthine) having an allyl ester structure were investigated in the presence of a Lewis acid in CH2Cl2. In the cases of uracil and N-4-acetylcytosine derivatives, SnCl4 appeared to be suitable, whereas the use of EtAlCl(2) was necessary for the hypoxanthine derivatives. The main pathway of these reactions was found to be a-face-selective S(N)2' allylic substitution, irrespective of the configuration of 2'-0-acyl leaving group. As a result, a new stereoselective operation for C-C bonds formation leading to 4'-carbon-substituted 2',3'-didehydro-2',3'-dideoxyribonucleosides has been disclosed for the first time. Stereochemistry of these 4'-C-branched products can be assigned on the basis of H-1 NMR spectroscopy in terms of the anisotropic shift of H-5 of the pyrimidine base (or H-8 of the hypoxanthine), which is caused by the 5'-0-(tert-butyldiphenylsilyl) protecting group.

  DOI：

  10.1021/jo9516190
• 作为产物：
  描述：

  1-(3,5-二甲氧基苯基)十七烷-1-醇 在 四氯化锡 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 生成 4'-C-allyl-N⁴,O^5'-diacetyl-2',3'-didehydro-2',3'-dideoxycytidine
  参考文献：
  名称：

  Allylic Substitution of 3‘,4‘-Unsaturated Nucleosides:  Organosilicon-Based Stereoselective Access to 4‘-C-Branched 2‘,3‘-Didehydro-2‘,3‘-dideoxyribonucleosides

  摘要：

  Reactions of organosilicon reagents (such as allyltrimethylsilane, silyl enol ethers, cyanotrimethylsilane) with 3',4'-unsaturated nucleosides (of uracil, N-4-acetylcytosine, and hypoxanthine) having an allyl ester structure were investigated in the presence of a Lewis acid in CH2Cl2. In the cases of uracil and N-4-acetylcytosine derivatives, SnCl4 appeared to be suitable, whereas the use of EtAlCl(2) was necessary for the hypoxanthine derivatives. The main pathway of these reactions was found to be a-face-selective S(N)2' allylic substitution, irrespective of the configuration of 2'-0-acyl leaving group. As a result, a new stereoselective operation for C-C bonds formation leading to 4'-carbon-substituted 2',3'-didehydro-2',3'-dideoxyribonucleosides has been disclosed for the first time. Stereochemistry of these 4'-C-branched products can be assigned on the basis of H-1 NMR spectroscopy in terms of the anisotropic shift of H-5 of the pyrimidine base (or H-8 of the hypoxanthine), which is caused by the 5'-0-(tert-butyldiphenylsilyl) protecting group.

  DOI：

  10.1021/jo9516190