(20S)-15β,16β:20,21-Diepoxy-3-<(tetrahydro-2H-pyran-2'-yl)oxy>-20-(trimethylsilyl)-5β,17α-pregnan-17-ol trifluoroacetate | 163431-32-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 类固醇和类固醇衍生物
• 英文名称: (20S)-15β,16β:20,21-Diepoxy-3-<(tetrahydro-2H-pyran-2'-yl)oxy>-20-(trimethylsilyl)-5β,17α-pregnan-17-ol trifluoroacetate
• 英文别名: [(1R,2S,3S,5S,6R,7S,10S,11S,14S,16R)-7,11-dimethyl-14-(oxan-2-yloxy)-6-[(2S)-2-trimethylsilyloxiran-2-yl]-4-oxapentacyclo[8.8.0.02,7.03,5.011,16]octadecan-6-yl] 2,2,2-trifluoroacetate
• CAS: 163431-32-1
• 化学式: C₃₁H₄₇F₃O₆Si
• 分子量: 600.791
• InChiKey: LYLXYWNDSMDLKV-VNDAQUCNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.42
• 重原子数：
  41
• 可旋转键数：
  6
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.97
• 拓扑面积：
  69.8
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  (20S)-15β,16β:20,21-Diepoxy-3-<(tetrahydro-2H-pyran-2'-yl)oxy>-20-(trimethylsilyl)-5β,17α-pregnan-17-ol trifluoroacetate 在 对甲苯磺酸 作用下， 以 甲醇 为溶剂， 反应 3.0h， 生成 Trifluoro-acetic acid (3S,5R,8R,9S,10S,13S,14S,15S,16S,17R)-3-hydroxy-10,13-dimethyl-17-((S)-2-trimethylsilanyl-oxiranyl)-hexadecahydro-20-oxa-cyclopropa[15,16]cyclopenta[a]phenanthren-17-yl ester
  参考文献：
  名称：

  Synthesis of Digitoxigenin from 3.beta.-Acetoxyandrost-5-en-17-one. Construction of a Suitably Functionalized Pregnane Side Chain via Presumed Allene Oxide Intermediate

  摘要：

  The synthesis of digitoxigenin (1) from 3 beta-acetoxyandrost-5-en-17-one (2) involves construction of the 21-hydroxy-20-keto pregnane side chain from 1-bromo-1-(trimethylsilyl)ethylene via presumed intermediate allene oxide 11. The key intermediate alcohol 10 is obtained by addition of 1-lithio-1-(trimethylsilyl)ethylene to the carbonyl group of 4 followed by selective epoxidations of the double bonds in 5. Reaction of trifluoroacetate 8 with aqueous tetra-n-butylammonium fluoride affords 15 beta,21-dihydroxypregn-16-en-20-one 12. After hydrogenation of the C-16,17 double bond, the butenolide ring is formed using (triphenylphosphoranylidene)ketene to give 15 beta-hydroxycardenolide 14, which has previously been converted to digitoxigenin (1).

  DOI：

  10.1021/jo00111a046
• 作为产物：
  描述：

  (20S)-15β,16β:20,21-Diepoxy-3-<(tetrahydro-2H-pyran-2'-yl)oxy>-20-(trimethylsilyl)-5β,17α-pregnan-17-ol 、 三氟乙酸酐 在 吡啶 作用下， 以92%的产率得到(20S)-15β,16β:20,21-Diepoxy-3-<(tetrahydro-2H-pyran-2'-yl)oxy>-20-(trimethylsilyl)-5β,17α-pregnan-17-ol trifluoroacetate
  参考文献：
  名称：

  Synthesis of Digitoxigenin from 3.beta.-Acetoxyandrost-5-en-17-one. Construction of a Suitably Functionalized Pregnane Side Chain via Presumed Allene Oxide Intermediate

  摘要：

  The synthesis of digitoxigenin (1) from 3 beta-acetoxyandrost-5-en-17-one (2) involves construction of the 21-hydroxy-20-keto pregnane side chain from 1-bromo-1-(trimethylsilyl)ethylene via presumed intermediate allene oxide 11. The key intermediate alcohol 10 is obtained by addition of 1-lithio-1-(trimethylsilyl)ethylene to the carbonyl group of 4 followed by selective epoxidations of the double bonds in 5. Reaction of trifluoroacetate 8 with aqueous tetra-n-butylammonium fluoride affords 15 beta,21-dihydroxypregn-16-en-20-one 12. After hydrogenation of the C-16,17 double bond, the butenolide ring is formed using (triphenylphosphoranylidene)ketene to give 15 beta-hydroxycardenolide 14, which has previously been converted to digitoxigenin (1).

  DOI：

  10.1021/jo00111a046