(-)-(1S,6R,6aS,7R)-6-(Benzoyloxy)-7-carbomethoxy-1-<(phenoxythiocarbonyl)oxy>hexahydro-1H-pyrrolizin-2-one | 158146-79-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (-)-(1S,6R,6aS,7R)-6-(Benzoyloxy)-7-carbomethoxy-1-<(phenoxythiocarbonyl)oxy>hexahydro-1H-pyrrolizin-2-one
• 英文别名: methyl (1R,2S,7R,8S)-7-benzoyloxy-3-oxo-2-phenoxycarbothioyloxy-1,2,5,6,7,8-hexahydropyrrolizine-1-carboxylate
• CAS: 158146-79-3
• 化学式: C₂₃H₂₁NO₇S
• 分子量: 455.488
• InChiKey: QLTORWNIDSPYKX-MKXGPGLRSA-N

物化性质

• 沸点：
  589.7±60.0 °C(predicted)
• 密度：
  1.41±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  32
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  124
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (-)-(1S,6R,6aS,7R)-6-(Benzoyloxy)-7-carbomethoxy-1-<(phenoxythiocarbonyl)oxy>hexahydro-1H-pyrrolizin-2-one 在 lithium aluminium tetrahydride 、 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 6.0h， 生成 矛裂碱
  参考文献：
  名称：

  The Tandem Cycloaddition Chemistry of Nitroalkenes. A Novel Synthesis of (-)-Hastanecine

  摘要：

  A short and efficient asymmetric synthesis of the pyrrolizidine necine base (-)-hastanecine is described. The key reaction in the synthesis is a sequential inter [4+2]/inter[3+2] cycloaddition. The Lewis acid promoted [4+2] cycloaddition between 2-acyloxy nitroalkene 16 and chiral vinyl ether 17 afforded a nitronate which underwent facile [3+2] cycloaddition with dimethyl maleate. The resulting nitroso acetal 19 had all the required stereocenters for (-)-hastanecine. The critical unmasking of the nitroso acetal 19 employed a hydrogenolytic cleavage to give the 1-azabicyclo-[3.3.0]octane skeleton of (-)-hastanecine.

  DOI：

  10.1021/jo00098a027
• 作为产物：
  描述：

  6-(Benzoyloxy)-7-carbomethoxy-1-hydroxyhexahydro-1H-pyrrolizin-2-one 、 硫代氯甲酸苯酯 在 吡啶 、 4-二甲氨基吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以82%的产率得到(-)-(1S,6R,6aS,7R)-6-(Benzoyloxy)-7-carbomethoxy-1-<(phenoxythiocarbonyl)oxy>hexahydro-1H-pyrrolizin-2-one
  参考文献：
  名称：

  The Tandem Cycloaddition Chemistry of Nitroalkenes. A Novel Synthesis of (-)-Hastanecine

  摘要：

  A short and efficient asymmetric synthesis of the pyrrolizidine necine base (-)-hastanecine is described. The key reaction in the synthesis is a sequential inter [4+2]/inter[3+2] cycloaddition. The Lewis acid promoted [4+2] cycloaddition between 2-acyloxy nitroalkene 16 and chiral vinyl ether 17 afforded a nitronate which underwent facile [3+2] cycloaddition with dimethyl maleate. The resulting nitroso acetal 19 had all the required stereocenters for (-)-hastanecine. The critical unmasking of the nitroso acetal 19 employed a hydrogenolytic cleavage to give the 1-azabicyclo-[3.3.0]octane skeleton of (-)-hastanecine.

  DOI：

  10.1021/jo00098a027

文献信息

• The Tandem Cycloaddition Chemistry of Nitroalkenes. A Novel Synthesis of (-)-Hastanecine
  作者：Scott E. Denmark、Atli Thorarensen

  DOI：10.1021/jo00098a027

  日期：1994.9

  A short and efficient asymmetric synthesis of the pyrrolizidine necine base (-)-hastanecine is described. The key reaction in the synthesis is a sequential inter [4+2]/inter[3+2] cycloaddition. The Lewis acid promoted [4+2] cycloaddition between 2-acyloxy nitroalkene 16 and chiral vinyl ether 17 afforded a nitronate which underwent facile [3+2] cycloaddition with dimethyl maleate. The resulting nitroso acetal 19 had all the required stereocenters for (-)-hastanecine. The critical unmasking of the nitroso acetal 19 employed a hydrogenolytic cleavage to give the 1-azabicyclo-[3.3.0]octane skeleton of (-)-hastanecine.