(4R,5S,7R,8R,9R,10S,13R,14R,16S)-13,20-Epoxy-16-ethoxy-21-nitrilopicrasa-2,11-diene | 155028-22-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (4R,5S,7R,8R,9R,10S,13R,14R,16S)-13,20-Epoxy-16-ethoxy-21-nitrilopicrasa-2,11-diene
• 英文别名: (1R,2R,4S,6R,8S,9R,13S,14R,17R)-4-ethoxy-9,13-dimethyl-5,18-dioxapentacyclo[12.5.0.01,6.02,17.08,13]nonadeca-10,15-diene-17-carbonitrile
• CAS: 155028-22-1
• 化学式: C₂₂H₂₉NO₃
• 分子量: 355.477
• InChiKey: REDDGJQTMVFQOO-PQNOTVSGSA-N

物化性质

• 沸点：
  490.1±45.0 °C(predicted)
• 密度：
  1.18±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  26
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  51.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (4R,5S,7R,8R,9R,10S,13R,14R,16S)-13,20-Epoxy-16-ethoxy-21-nitrilopicrasa-2,11-diene 在 氢氧化钾 、 双氧水 作用下， 以 1,4-二氧六环 为溶剂， 反应 0.25h， 生成 (4R,5S,7R,8R,9R,10S,13R,14R,16S)-13,20-Epoxy-16-ethoxypicrasa-2,11-dien-21-oic acid
  参考文献：
  名称：

  Synthesis of 15-deoxy-16.beta.-ethoxybruceantin and synthetic efforts toward bruceantin

  摘要：

  Utilization of asymmetric Michael addition leads to chiral phenanthrenone (+)-4 suitable for the synthesis of Bruceantin. The D-ring is assembled by means of an intramolecular alkylation of the bromoacetals 25 while only the axial diastereomer 25ax proceeds smoothly. The formation of the cyanohydrin introduces the C-13 carborxyl group and tandem intramolecular alkylation provides the furan E-ring. The C-11,12 cis-diol 39 is readily transformed to the trans-diol 42 via an unusual Swern-type oxidation/reduction sequence. The C-2,3 olefin proves to be an efficient progenitor for the A-ring diosphenol function which can be introduced at the late stage of the synthesis. 15-Deoxy-16 beta-ethoxybruceantin 3 is accordingly prepared. Attempts to elaborate common intermediates toward the synthesis of bruceantin are described. The presence of an oxygen function at C-15 drastically changes the relative reactivity of the C-2,3 and C-11,12 olefinic bonds.

  DOI：

  10.1021/jo00081a008
• 作为产物：
  描述：

  (4R,5S,7R,8R,9R,10S,12R,13R,14R,16S)-13,20-Epoxy-16-ethoxy-12-(phenylseleno)-21-nitrilopicrasa-2-ene 在 双氧水 、 碳酸氢钠 作用下， 以 四氢呋喃 为溶剂， 反应 30.0h， 生成 (4R,5S,7R,8R,9R,10S,13R,14R,16S)-13,20-Epoxy-16-ethoxy-21-nitrilopicrasa-2,11-diene
  参考文献：
  名称：

  Synthesis of 15-deoxy-16.beta.-ethoxybruceantin and synthetic efforts toward bruceantin

  摘要：

  Utilization of asymmetric Michael addition leads to chiral phenanthrenone (+)-4 suitable for the synthesis of Bruceantin. The D-ring is assembled by means of an intramolecular alkylation of the bromoacetals 25 while only the axial diastereomer 25ax proceeds smoothly. The formation of the cyanohydrin introduces the C-13 carborxyl group and tandem intramolecular alkylation provides the furan E-ring. The C-11,12 cis-diol 39 is readily transformed to the trans-diol 42 via an unusual Swern-type oxidation/reduction sequence. The C-2,3 olefin proves to be an efficient progenitor for the A-ring diosphenol function which can be introduced at the late stage of the synthesis. 15-Deoxy-16 beta-ethoxybruceantin 3 is accordingly prepared. Attempts to elaborate common intermediates toward the synthesis of bruceantin are described. The presence of an oxygen function at C-15 drastically changes the relative reactivity of the C-2,3 and C-11,12 olefinic bonds.

  DOI：

  10.1021/jo00081a008