(4R,5S,7R,8R,9R,10S,12S,14R,16S)-20-(Methanesulfonyl)-16-ethoxy-13-oxo-12-(phenylseleno)-21-norpicras-2-ene | 155039-11-5

• 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,12S,14R,16S)-20-(Methanesulfonyl)-16-ethoxy-13-oxo-12-(phenylseleno)-21-norpicras-2-ene
• 英文别名: [(1R,2S,6R,7S,9R,11S,13R,15S,17R)-11-ethoxy-2,6-dimethyl-14-oxo-15-phenylselanyl-10-oxatetracyclo[7.7.1.02,7.013,17]heptadec-4-en-17-yl]methyl methanesulfonate
• CAS: 155039-11-5
• 化学式: C₂₈H₃₈O₆SSe
• 分子量: 581.632
• InChiKey: AGNMMRDZUVVLEJ-VDWSCZKUSA-N

物化性质

• 沸点：
  672.8±55.0 °C(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.75
• 重原子数：
  36
• 可旋转键数：
  7
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  87.3
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (4R,5S,7R,8R,9R,10S,12S,14R,16S)-20-(Methanesulfonyl)-16-ethoxy-13-oxo-12-(phenylseleno)-21-norpicras-2-ene 在 吡啶 、 氢氧化钾 、 18-冠醚-6 、 双氧水 、 4-甲基苯磺酸吡啶 、 碳酸氢钠 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 乙醚 、 二氯甲烷 、 甲苯 、 乙腈 为溶剂， 反应 46.25h， 生成 (4R^*,5S^*,7R^*,8R^*,9R^*,10S^*,13R^*,14R^*)-13,20-Epoxypicras-2,11,15-trien-21-oic acid methyl ester
  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：

  (1S,2S,4aS,4bR,9R,10aS)-1,2,3,4,4a,4b,5,6,7,9,10,10a-Dodecahydro-9-hydroxy-2-(methanesulfonyl)-1,4a-dimethylphenanthren-7-one 在 咪唑 、 盐酸 、 potassium cyanide 、 sodium tetrahydroborate 、 18-冠醚-6 、 potassium tert-butylate 、 四丁基氟化铵 、 氨 、 双氧水 、 溴 、 四丁基碘化铵 、 lithium 、 sodium hydride 、 二异丁基氢化铝 、 碳酸氢钠 、 三乙胺 、 2,3-二甲基苯胺 作用下， 以 四氢呋喃 、 乙醚 、 乙醇 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 、 苯 为溶剂， 反应 214.25h， 生成 (4R,5S,7R,8R,9R,10S,12S,14R,16S)-20-(Methanesulfonyl)-16-ethoxy-13-oxo-12-(phenylseleno)-21-norpicras-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

文献信息

• Synthesis of 15-deoxy-16.beta.-ethoxybruceantin and synthetic efforts toward bruceantin
  作者：Charles K.-F. Chiu、S. V. Govindan、P. L. Fuchs

  DOI：10.1021/jo00081a008

  日期：1994.1

  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.