8-O-tert-butyl 3-O-methyl (1R,5S)-2-hydroxy-8-azabicyclo[3.2.1]oct-2-ene-3,8-dicarboxylate | 208037-90-5

• 分子结构分类: 有机化合物 - 生物碱及其衍生物
• 英文名称: 8-O-tert-butyl 3-O-methyl (1R,5S)-2-hydroxy-8-azabicyclo[3.2.1]oct-2-ene-3,8-dicarboxylate
• CAS: 208037-90-5
• 化学式: C₁₄H₂₁NO₅
• 分子量: 283.324
• InChiKey: WDWDZTUGCCMYSM-WCBMZHEXSA-N

物化性质

• 沸点：
  393.5±42.0 °C(Predicted)
• 密度：
  1.258±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  76.1
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  8-O-tert-butyl 3-O-methyl (1R,5S)-2-hydroxy-8-azabicyclo[3.2.1]oct-2-ene-3,8-dicarboxylate 在 sodium iodide 作用下， 以 吡啶 、 甲醇 为溶剂， 反应 9.5h， 生成 (1R,5S)-8-(tert-butyloxycarbonyl)-8-azabicyclo[3.2.1]-2-octanone p-tosylhydrazone
  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：

  (2R,5S)-N-(tert-butyloxycarbonyl)-5-[1'-(2'-methoxycarbonyl)ethyl]proline methyl ester 在 双(三甲基硅烷基)氨基钾 作用下， 以 四氢呋喃 为溶剂， 反应 6.0h， 以85%的产率得到8-O-tert-butyl 3-O-methyl (1R,5S)-2-hydroxy-8-azabicyclo[3.2.1]oct-2-ene-3,8-dicarboxylate
  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