(4R,5S,7R,8R,9R,10S,12R,13R,14R,16S)-13,20-Epoxy-16-ethoxy-12-(phenylseleno)-21-nitrilopicrasa-2-ene | 155028-21-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 萘并呋喃类
• 英文名称: (4R,5S,7R,8R,9R,10S,12R,13R,14R,16S)-13,20-Epoxy-16-ethoxy-12-(phenylseleno)-21-nitrilopicrasa-2-ene
• 英文别名: (1R,2R,4S,6R,8S,9R,13S,14R,16R,17R)-4-ethoxy-9,13-dimethyl-16-phenylselanyl-5,18-dioxapentacyclo[12.5.0.01,6.02,17.08,13]nonadec-10-ene-17-carbonitrile
• CAS: 155028-21-0
• 化学式: C₂₈H₃₅NO₃Se
• 分子量: 512.551
• InChiKey: YUYSMKRXLMGJBK-IDKJJPSZSA-N

物化性质

• 沸点：
  612.0±55.0 °C(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.49
• 重原子数：
  33
• 可旋转键数：
  4
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.68
• 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,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
• 作为产物：
  描述：

  (4R,5S,7R,8R,9R,10S,14R,16S)-20-<(Benzyloxy)methyl>-16-ethoxy-13-oxo-21-norpicras-2-ene 在 18-冠醚-6 、 氨 、 lithium 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙腈 为溶剂， 反应 18.75h， 生成 (4R,5S,7R,8R,9R,10S,12R,13R,14R,16S)-13,20-Epoxy-16-ethoxy-12-(phenylseleno)-21-nitrilopicrasa-2-ene
  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