(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 | 155028-02-7

• 英文名称: (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
• 英文别名: [(1S,2S,4aS,4bR,9R,10aS)-9-hydroxy-1,4a-dimethyl-7-oxo-1,2,3,4,4b,5,6,9,10,10a-decahydrophenanthren-2-yl] methanesulfonate
• CAS: 155028-02-7
• 化学式: C₁₇H₂₆O₅S
• 分子量: 342.456
• InChiKey: DKCVBYUOMQYXHN-XMWZSSCBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  89
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  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 、 potassium cyanide 、 sodium tetrahydroborate 、 18-冠醚-6 、 双氧水 、 碳酸氢钠 、 三乙胺 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 、 苯 为溶剂， 反应 139.0h， 生成 (1R,4aS,4bR,8aS,9R,10aS)-7,9-bis[[tert-butyl(dimethyl)silyl]oxy]-1,4a-dimethyl-1,4,4b,5,8,9,10,10a-octahydrophenanthrene-8a-carbonitrile
  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 Oxone 、 氨 、 4-甲基苯磺酸吡啶 、 lithium 、 碳酸氢钠 、 三乙胺 、 叔丁醇 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 二氯甲烷 、 水 为溶剂， 反应 9.33h， 生成 (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
  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