3β-<(Tetrahydro-2H-pyran-2'-yl)oxy>-5β-androst-15-en-17-one

• 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: 3β-<(Tetrahydro-2H-pyran-2'-yl)oxy>-5β-androst-15-en-17-one
• 英文别名: (3S,5R,8R,9S,10S,13S,14S)-10,13-dimethyl-3-(oxan-2-yloxy)-1,2,3,4,5,6,7,8,9,11,12,14-dodecahydrocyclopenta[a]phenanthren-17-one
• 化学式: C₂₄H₃₆O₃
• 分子量: 372.548
• InChiKey: ACXXSGFNJCISSL-NFPCVBQDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  27
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1-溴乙烯基)三甲硅烷 、 3β-<(Tetrahydro-2H-pyran-2'-yl)oxy>-5β-androst-15-en-17-one 在 正丁基锂 、 三氟化硼乙醚 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以91%的产率得到3β-<(Tetrahydro-2H-pyran-2'-yl)oxy>-20-(trimethylsilyl)-5β,17α-pregna-15,20-dien-17-ol
  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：

  3,4-二氢-2H-吡喃 、 3β-hydroxy-5β-androst-15-en-17-one 在 对甲苯磺酸 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以88%的产率得到3β-<(Tetrahydro-2H-pyran-2'-yl)oxy>-5β-androst-15-en-17-one
  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

文献信息

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

  DOI：10.1021/jo00111a046

  日期：1995.3

  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).