(4R,5S,7R,8R,9R,10S,14R,16S)-20-(Methanesulfonyl)-13-<(tert-butyldimethylsilyl)oxy>-16-ethoxy-21-norpicras-2,12-diene | 155028-19-6

• 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,14R,16S)-20-(Methanesulfonyl)-13-<(tert-butyldimethylsilyl)oxy>-16-ethoxy-21-norpicras-2,12-diene
• 英文别名: (4R,5S,7R,8R,9R,10S,14R,16S)-20-(Methanesulfonyl)-13-[(tert-butyldimethylsilyl)oxy]-16-ethoxy-21-norpicras-2,12-diene；[(1R,2S,6R,7S,9R,11S,13R,17R)-14-[tert-butyl(dimethyl)silyl]oxy-11-ethoxy-2,6-dimethyl-10-oxatetracyclo[7.7.1.02,7.013,17]heptadeca-4,14-dien-17-yl]methyl methanesulfonate
• CAS: 155028-19-6
• 化学式: C₂₈H₄₈O₆SSi
• 分子量: 540.837
• InChiKey: MGEPJKLNAPSMSY-QKQRTDJFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.26
• 重原子数：
  36
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  79.4
• 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,14R,16S)-20-(Methanesulfonyl)-13-<(tert-butyldimethylsilyl)oxy>-16-ethoxy-21-norpicras-2,12-diene 在 18-冠醚-6 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 15.5h， 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
• 作为产物：
  描述：

  (S)-(-)-2,3,4,4a,9,10-hexahydro-7-methoxy-1,4a-dimethyl-2-oxophenanthrene 在 咪唑 、 盐酸 、 potassium cyanide 、 Oxone 、 sodium tetrahydroborate 、 18-冠醚-6 、 potassium tert-butylate 、 四丁基氟化铵 、 氨 、 双氧水 、 溴 、 4-甲基苯磺酸吡啶 、 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 、 叔丁醇 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 乙醚 、 乙醇 、 正己烷 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 甲苯 、 苯 为溶剂， 反应 223.08h， 生成 (4R,5S,7R,8R,9R,10S,14R,16S)-20-(Methanesulfonyl)-13-<(tert-butyldimethylsilyl)oxy>-16-ethoxy-21-norpicras-2,12-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

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.