20-Deethyl-1,2,16,17-tetradehydro-5-oxoaspidospermidine

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 鸡蛋花型生物碱
• 英文名称: 20-Deethyl-1,2,16,17-tetradehydro-5-oxoaspidospermidine
• 英文别名: (1R,12S,19S)-8,16-diazapentacyclo[10.6.1.01,9.02,7.016,19]nonadeca-2,4,6,8,10-pentaen-17-one
• 化学式: C₁₇H₁₆N₂O
• 分子量: 264.327
• InChiKey: YXQIEJYWCRJZRG-GOPGUHFVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  20
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  32.7
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  20-Deethyl-1,2,16,17-tetradehydro-5-oxoaspidospermidine 在 lithium aluminium tetrahydride 、 potassium tert-butylate 作用下， 以 四氢呋喃 、 乙二醇 、 苯 为溶剂， 反应 47.0h， 生成 aspidospermidine
  参考文献：
  名称：

  Total Synthesis of (.+-.)-Aspidofractinine and (.+-.)-Aspidospermidine

  摘要：

  Functional group manipulations on a previously constructed, easily accessible deethylaspidospermidine derivative have transformed the latter in few steps into a ring E diene, whose Diels-Alder reaction with phenyl vinyl sulfone and subsequent reductions has led to (+/-)-aspidofractinine. One-bond unraveling of a (phenylsulfonyl)aspidofractinine intermediate, followed by reductions, provided a second-generation pathway to (+/-)-aspidospermidine.

  DOI：

  10.1021/jo00104a023
• 作为产物：
  描述：

  20-deethyl-2,16-didehydro-5,17-dioxo-1-(p-tolylsulfonyl)aspidospermidine 在 sodium tetrahydroborate 、 cerium(III) chloride 、 三氟化硼乙醚 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 8.17h， 生成 20-Deethyl-1,2,16,17-tetradehydro-5-oxoaspidospermidine
  参考文献：
  名称：

  Total Synthesis of (.+-.)-Aspidofractinine and (.+-.)-Aspidospermidine

  摘要：

  Functional group manipulations on a previously constructed, easily accessible deethylaspidospermidine derivative have transformed the latter in few steps into a ring E diene, whose Diels-Alder reaction with phenyl vinyl sulfone and subsequent reductions has led to (+/-)-aspidofractinine. One-bond unraveling of a (phenylsulfonyl)aspidofractinine intermediate, followed by reductions, provided a second-generation pathway to (+/-)-aspidospermidine.

  DOI：

  10.1021/jo00104a023

文献信息

• Stereoselective Synthesis of (+)-Aspidofractinine
  作者：David Gagnon、Claude Spino

  DOI：10.1021/jo9009497

  日期：2009.8.21

  We describe the synthesis of (+)-aspidofractinine, the enantiomer of a naturally occurring alkaloid of the kopsane family. Key features of the synthesis include a stereospecific cyanate to isocyanate rearrangement on a chiral scaffold, a ring-closing alkene metathesis to cleave the chiral auxiliary, and a chemoselective cyclopropanation to introduce the quaternary carbon at position 7 of aspidofractinine

  我们描述了（+）-aspidofractinine的合成，这是自然的kopsane家族生物碱的对映异构体。合成的关键特征包括在手性支架上将立体特异性氰酸酯重排成异氰酸酯，闭环的烯烃复分解以裂解手性助剂，以及化学选择性的环丙烷化以将季碳原子引入Aspidofractinine的7位。
• Total Synthesis of (.+-.)-Aspidofractinine and (.+-.)-Aspidospermidine
  作者：Ernest Wenkert、Song Liu

  DOI：10.1021/jo00104a023

  日期：1994.12

  Functional group manipulations on a previously constructed, easily accessible deethylaspidospermidine derivative have transformed the latter in few steps into a ring E diene, whose Diels-Alder reaction with phenyl vinyl sulfone and subsequent reductions has led to (+/-)-aspidofractinine. One-bond unraveling of a (phenylsulfonyl)aspidofractinine intermediate, followed by reductions, provided a second-generation pathway to (+/-)-aspidospermidine.