3'-azido-3'-deoxy-5'-O--3-methylthymidine | 148380-00-1

• 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'-azido-3'-deoxy-5'-O--3-methylthymidine
• 英文别名: 3'-azido-3'-deoxy-5'-O-[dimethyl(1,1,2,trimethylpropyl)silyl]-3-methylthymidine；1-[(2R,4S,5S)-4-azido-5-[[2,3-dimethylbutan-2-yl(dimethyl)silyl]oxymethyl]oxolan-2-yl]-3,5-dimethylpyrimidine-2,4-dione
• CAS: 148380-00-1
• 化学式: C₁₉H₃₃N₅O₄Si
• 分子量: 423.588
• InChiKey: LJFSPRZKLWDYHJ-ARFHVFGLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.48
• 重原子数：
  29
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  73.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3'-azido-3'-deoxy-5'-O--3-methylthymidine 在 甲醇 、 Dowex 50WX₂(H⁺) beads 作用下， 以70%的产率得到3'-azido-3'-deoxy-3-methylthymidine
  参考文献：
  名称：

  N- versus O-Alkylation of 2,3'-anhydrothymidine: reaction of the obtained pyrimidinium salts with azide ion

  摘要：

  Reaction of 5'-O-(thexyldimethylsilyl)anhydrothymidine (1) with O-(mesitylenesulfonyl)hydroxylamine and CH3OTf generates the pyrimidinium salts 3a and 3b which react with azide ion to give the N3-substituted AZT derivatives 4a and 4b, respectively. In contrast, alkylation of 1 with pentyl triflate occurs at both the N3 and 04 positions leading, after treatment with NaN3, to the expected AZT analog 4d and the novel 3-substituted 2,3-dideoxyxylofuranosyl azide 7d. In a further study, the extent to which competing 04-alkylation occurs was found to be sensitive to steric factors, increasing in the order MeOTf < EtOTf < pentyl OTf < i-PrOTf. Formation of the alternate 04-alkylated AZT derivatives 9 via an intramolecular Hilbert-Johnson process was not observed in these reactions. It was demonstrated, however, that reaction of the intermediate O4-alkylated pyridinium salt 6c with Me4NCl does evolve toward the corresponding C-3' chloro compound 14c. Reaction of 1 with the less reactive alkylating agent (EtO)2P(O)CH2OTf is more complicated producing the O-alkylated product 7f and the novel dimer 19.

  DOI：

  10.1021/jo00063a021
• 作为产物：
  描述：

  (1R,9R,10R)-10-[[2,3-dimethylbutan-2-yl(dimethyl)silyl]oxymethyl]-4,6-dimethyl-8,11-dioxa-6-aza-2-azoniatricyclo[7.2.1.02,7]dodeca-2(7),3-dien-5-one;trifluoromethanesulfonate 在 sodium azide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 3'-azido-3'-deoxy-5'-O--3-methylthymidine
  参考文献：
  名称：

  N- versus O-Alkylation of 2,3'-anhydrothymidine: reaction of the obtained pyrimidinium salts with azide ion

  摘要：

  Reaction of 5'-O-(thexyldimethylsilyl)anhydrothymidine (1) with O-(mesitylenesulfonyl)hydroxylamine and CH3OTf generates the pyrimidinium salts 3a and 3b which react with azide ion to give the N3-substituted AZT derivatives 4a and 4b, respectively. In contrast, alkylation of 1 with pentyl triflate occurs at both the N3 and 04 positions leading, after treatment with NaN3, to the expected AZT analog 4d and the novel 3-substituted 2,3-dideoxyxylofuranosyl azide 7d. In a further study, the extent to which competing 04-alkylation occurs was found to be sensitive to steric factors, increasing in the order MeOTf < EtOTf < pentyl OTf < i-PrOTf. Formation of the alternate 04-alkylated AZT derivatives 9 via an intramolecular Hilbert-Johnson process was not observed in these reactions. It was demonstrated, however, that reaction of the intermediate O4-alkylated pyridinium salt 6c with Me4NCl does evolve toward the corresponding C-3' chloro compound 14c. Reaction of 1 with the less reactive alkylating agent (EtO)2P(O)CH2OTf is more complicated producing the O-alkylated product 7f and the novel dimer 19.

  DOI：

  10.1021/jo00063a021

文献信息

• N- versus O-Alkylation of 2,3'-anhydrothymidine: reaction of the obtained pyrimidinium salts with azide ion
  作者：Catherine Goulaouic、David R. Adams、Angele Chiaroni、Claude Riche、David S. Grierson

  DOI：10.1021/jo00063a021

  日期：1993.5

  Reaction of 5'-O-(thexyldimethylsilyl)anhydrothymidine (1) with O-(mesitylenesulfonyl)hydroxylamine and CH3OTf generates the pyrimidinium salts 3a and 3b which react with azide ion to give the N3-substituted AZT derivatives 4a and 4b, respectively. In contrast, alkylation of 1 with pentyl triflate occurs at both the N3 and 04 positions leading, after treatment with NaN3, to the expected AZT analog 4d and the novel 3-substituted 2,3-dideoxyxylofuranosyl azide 7d. In a further study, the extent to which competing 04-alkylation occurs was found to be sensitive to steric factors, increasing in the order MeOTf < EtOTf < pentyl OTf < i-PrOTf. Formation of the alternate 04-alkylated AZT derivatives 9 via an intramolecular Hilbert-Johnson process was not observed in these reactions. It was demonstrated, however, that reaction of the intermediate O4-alkylated pyridinium salt 6c with Me4NCl does evolve toward the corresponding C-3' chloro compound 14c. Reaction of 1 with the less reactive alkylating agent (EtO)2P(O)CH2OTf is more complicated producing the O-alkylated product 7f and the novel dimer 19.