(3S,5R)-5-[[[(1,1-dimethylethyl)dimethylsilyl]oxy]methyl]tetrahydrofuran-3-ol | 204509-02-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧唑烯
• 英文名称: (3S,5R)-5-[[[(1,1-dimethylethyl)dimethylsilyl]oxy]methyl]tetrahydrofuran-3-ol
• 英文别名: (3S,5R)-5-[[tert-butyl(dimethyl)silyl]oxymethyl]oxolan-3-ol
• CAS: 204509-02-4
• 化学式: C₁₁H₂₄O₃Si
• 分子量: 232.395
• InChiKey: QCBSCBSZTOONKN-VHSXEESVSA-N

物化性质

• 沸点：
  277.6±20.0 °C(Predicted)
• 密度：
  0.972±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.16
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3S,5R)-5-[[[(1,1-dimethylethyl)dimethylsilyl]oxy]methyl]tetrahydrofuran-3-ol 在 4-二甲氨基吡啶 、 18-冠醚-6 、 potassium carbonate 、 三乙胺 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 30.0h， 生成 6-amino-9-[(3R,5R)-5-[[[(1,1-dimethylethyl)dimethylsilyl]oxy]methyl]tetrahydrofuran-3-yl]purine
  参考文献：
  名称：

  Enantiospecific Total Synthesis of l-2‘,3‘-Dideoxyisonucleosides via Regioselective Opening of Optically Active C₂-Symmetric 1,4-Pentadiene Bis-epoxide¹

  摘要：

  A new method for the synthesis of L-2',3'-dideoxyisonucleosides is described. The readily available, optically active C-2-symmetric bis-epoxide (2S,4S)-1,2:4,5-diepoxypentane (5) was prepared by a short route from readily available starting materials. The key step of the new synthesis is the opening of 5 with nucleophiles, which proceeds highly regioselectively; e.g., reaction with sodium sulfide affords a 5:1 mixture of the tetrahydrothiophenediol 9a and the tetrahydrothiopyrandiol 14, and reaction with sodium hydroxide gives exclusively the tetrahydrofurandiol 9b via a preferred 5-exo cyclization. These five-membered diols 9a,b can be converted in only four steps into the modified dideoxyuridine and adenosine isonucleosides 4a-c, one of which (4c) has shown good antiviral activity. In addition, we have examined the opening of the analogous six carbon bis-epoxide, (2S,5S)-1,2:5,6-diepoxyhexane (23), which affords a 3:1 mixture of the hexahydrothiepinediol 24 and the tetrahydrothiopyrandiol 25 with sodium sulfide via a preferred 7-endo cyclization. An alternate route to these two optically active bis-epoxides 5 and 23 was also examined, namely the asymmetric dihydroxylation of 1,4-pentadiene and 1,5-hexadiene followed by selective sulfonylation and epoxide : formation. The asymmetric reaction produces a nearly 1:1 mixture of optically active and meso tetrols, e.g., 28-9 and 32-3. Unfortunately, the tetrols, their simple derivatives, and the final sulfonates and epoxides could not be readily separated by Rnv simple means.

  DOI：

  10.1021/jo9721655
• 作为产物：
  描述：

  1,4-戊二烯 在 potassium osmate(VI) 、 氢化奎宁 1,4-(2,3-二氮杂萘)二醚 吡啶 、 4-二甲氨基吡啶 、 sodium hydroxide 、 sodium hydride 、 potassium carbonate 、 三乙胺 、 potassium hexacyanoferrate(III) 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 叔丁醇 为溶剂， 反应 71.0h， 生成 (3S,5R)-5-[[[(1,1-dimethylethyl)dimethylsilyl]oxy]methyl]tetrahydrofuran-3-ol
  参考文献：
  名称：

  Enantiospecific Total Synthesis of l-2‘,3‘-Dideoxyisonucleosides via Regioselective Opening of Optically Active C₂-Symmetric 1,4-Pentadiene Bis-epoxide¹

  摘要：

  A new method for the synthesis of L-2',3'-dideoxyisonucleosides is described. The readily available, optically active C-2-symmetric bis-epoxide (2S,4S)-1,2:4,5-diepoxypentane (5) was prepared by a short route from readily available starting materials. The key step of the new synthesis is the opening of 5 with nucleophiles, which proceeds highly regioselectively; e.g., reaction with sodium sulfide affords a 5:1 mixture of the tetrahydrothiophenediol 9a and the tetrahydrothiopyrandiol 14, and reaction with sodium hydroxide gives exclusively the tetrahydrofurandiol 9b via a preferred 5-exo cyclization. These five-membered diols 9a,b can be converted in only four steps into the modified dideoxyuridine and adenosine isonucleosides 4a-c, one of which (4c) has shown good antiviral activity. In addition, we have examined the opening of the analogous six carbon bis-epoxide, (2S,5S)-1,2:5,6-diepoxyhexane (23), which affords a 3:1 mixture of the hexahydrothiepinediol 24 and the tetrahydrothiopyrandiol 25 with sodium sulfide via a preferred 7-endo cyclization. An alternate route to these two optically active bis-epoxides 5 and 23 was also examined, namely the asymmetric dihydroxylation of 1,4-pentadiene and 1,5-hexadiene followed by selective sulfonylation and epoxide : formation. The asymmetric reaction produces a nearly 1:1 mixture of optically active and meso tetrols, e.g., 28-9 and 32-3. Unfortunately, the tetrols, their simple derivatives, and the final sulfonates and epoxides could not be readily separated by Rnv simple means.

  DOI：

  10.1021/jo9721655

文献信息

• Enantiospecific Total Synthesis of <scp>l</scp>-2‘,3‘-Dideoxyisonucleosides via Regioselective Opening of Optically Active <i>C</i>₂-Symmetric 1,4-Pentadiene Bis-epoxide¹
  作者：Michael E. Jung、Oliver Kretschik

  DOI：10.1021/jo9721655

  日期：1998.5.1

  A new method for the synthesis of L-2',3'-dideoxyisonucleosides is described. The readily available, optically active C-2-symmetric bis-epoxide (2S,4S)-1,2:4,5-diepoxypentane (5) was prepared by a short route from readily available starting materials. The key step of the new synthesis is the opening of 5 with nucleophiles, which proceeds highly regioselectively; e.g., reaction with sodium sulfide affords a 5:1 mixture of the tetrahydrothiophenediol 9a and the tetrahydrothiopyrandiol 14, and reaction with sodium hydroxide gives exclusively the tetrahydrofurandiol 9b via a preferred 5-exo cyclization. These five-membered diols 9a,b can be converted in only four steps into the modified dideoxyuridine and adenosine isonucleosides 4a-c, one of which (4c) has shown good antiviral activity. In addition, we have examined the opening of the analogous six carbon bis-epoxide, (2S,5S)-1,2:5,6-diepoxyhexane (23), which affords a 3:1 mixture of the hexahydrothiepinediol 24 and the tetrahydrothiopyrandiol 25 with sodium sulfide via a preferred 7-endo cyclization. An alternate route to these two optically active bis-epoxides 5 and 23 was also examined, namely the asymmetric dihydroxylation of 1,4-pentadiene and 1,5-hexadiene followed by selective sulfonylation and epoxide : formation. The asymmetric reaction produces a nearly 1:1 mixture of optically active and meso tetrols, e.g., 28-9 and 32-3. Unfortunately, the tetrols, their simple derivatives, and the final sulfonates and epoxides could not be readily separated by Rnv simple means.