tert-butyl (1R,2R,3S,5S)-2-carbamoyl-3-hydroxy-8-azabicyclo[3.2.1]octane-8-carboxylate | 208037-86-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: tert-butyl (1R,2R,3S,5S)-2-carbamoyl-3-hydroxy-8-azabicyclo[3.2.1]octane-8-carboxylate
• CAS: 208037-86-9
• 化学式: C₁₃H₂₂N₂O₄
• 分子量: 270.329
• InChiKey: LOVCDKNNQWEYFT-QCLAVDOMSA-N

物化性质

• 熔点：
  153-154 °C
• 沸点：
  465.4±45.0 °C(Predicted)
• 密度：
  1.248±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  92.9
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  tert-butyl (1R,2R,3S,5S)-2-carbamoyl-3-hydroxy-8-azabicyclo[3.2.1]octane-8-carboxylate 在 4-二甲氨基吡啶 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 13.0h， 生成 [(1R,2R,3S,5S)-2-carbamoyl-8-azabicyclo[3.2.1]octan-3-yl] benzoate
  参考文献：
  名称：

  Enantiospecific Synthesis of Natural (−)-Cocaine and Unnatural (+)-Cocaine from d- and l-Glutamic Acid

  摘要：

  Natural (-)-cocaine and unnatural (+)-cocaine have been synthesized enantiospecifically from D- and L-glutamic acid, respectively. The axial-equatorial substitutents were introduced by a stereo- and regiospecific dipolar cycloaddition to the corresponding (LR,5S)- and (1S,5R)-N-BOC-nortropenes with (ethoxycarbonyl)formonitrile N-oxide. A sequence of subsequent stereochemically controlled transformations converted the fused isoxazoline to the requisite P-hydroxy ester. Synthesis of the key intermediate N-BOC-nortropenes involved construction of the 8-azabicyclo[3.2.1]octane framework by Dieckmann condensation of cis-5-substituted D-and L-proline esters. For comparison, (1R,SS)-N-BOC-nortropene also was derived by degradation from natural cocaine. The cis-5-substituted D-and L-proline esters were obtained by sulfide contraction and subsequent catalytic hydrogenation to induce stereospecifically the C-5 stereochemistry from D-and L-thiopyroglutamate, which in turn were prepared from D-and L-glutamic acids, respectively.

  DOI：

  10.1021/jo980153t
• 作为产物：
  描述：

  11-O-tert-butyl 3-O-ethyl (1R,2S,6S,8S)-5-oxa-4,11-diazatricyclo[6.2.1.02,6]undec-3-ene-3,11-dicarboxylate 在 sodium hydroxide 、 双氧水 、 sodium carbonate 作用下， 以 乙醇 、 水 为溶剂， 反应 27.17h， 生成 tert-butyl (1R,2R,3S,5S)-2-carbamoyl-3-hydroxy-8-azabicyclo[3.2.1]octane-8-carboxylate
  参考文献：
  名称：

  Enantiospecific Synthesis of Natural (−)-Cocaine and Unnatural (+)-Cocaine from d- and l-Glutamic Acid

  摘要：

  Natural (-)-cocaine and unnatural (+)-cocaine have been synthesized enantiospecifically from D- and L-glutamic acid, respectively. The axial-equatorial substitutents were introduced by a stereo- and regiospecific dipolar cycloaddition to the corresponding (LR,5S)- and (1S,5R)-N-BOC-nortropenes with (ethoxycarbonyl)formonitrile N-oxide. A sequence of subsequent stereochemically controlled transformations converted the fused isoxazoline to the requisite P-hydroxy ester. Synthesis of the key intermediate N-BOC-nortropenes involved construction of the 8-azabicyclo[3.2.1]octane framework by Dieckmann condensation of cis-5-substituted D-and L-proline esters. For comparison, (1R,SS)-N-BOC-nortropene also was derived by degradation from natural cocaine. The cis-5-substituted D-and L-proline esters were obtained by sulfide contraction and subsequent catalytic hydrogenation to induce stereospecifically the C-5 stereochemistry from D-and L-thiopyroglutamate, which in turn were prepared from D-and L-glutamic acids, respectively.

  DOI：

  10.1021/jo980153t