(E)-17-<(Diethylphosphono)isocyanomethylene>-3-methoxyandrosta-3,5-diene | 139527-68-7

• 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: (E)-17-<(Diethylphosphono)isocyanomethylene>-3-methoxyandrosta-3,5-diene
• 英文别名: (E)-17-<(diethylphosphono)isocanomethylene>-3-methoxyandrosta-3,5-diene；(E)-17-[(Diethylphosphono)isocyanomethylene]-3-methoxyandrosta-3,5-diene；(E)-17-[(diethylphosphono)isocanomethylene]-3-methoxyandrosta-3,5-diene；(8R,9S,10R,13S,14S,17E)-17-[diethoxyphosphoryl(isocyano)methylidene]-3-methoxy-10,13-dimethyl-1,2,7,8,9,11,12,14,15,16-decahydrocyclopenta[a]phenanthrene
• CAS: 139527-68-7
• 化学式: C₂₆H₃₈NO₄P
• 分子量: 459.566
• InChiKey: WXHZNYMHTWUDHT-LNTLRLOASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  32
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  49.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (E)-17-<(Diethylphosphono)isocyanomethylene>-3-methoxyandrosta-3,5-diene 在 sodium tetrahydroborate 、 高氯酸 、 potassium tert-butylate 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 乙醇 为溶剂， 反应 3.42h， 生成 黄体酮
  参考文献：
  名称：

  Chemistry of N,P-acetals: application to the synthesis of 20-ketosteroids

  摘要：

  A series of new derivatives of alpha-(isocyanomethyl)phosphonates (6a,b,c and 9) is described, which are formed by methylation of (E)-17-[(diethylphosphono)isocyanomethylene] steroids 5a,b,c and 17-beta-[(diethylphosphono)isocyanomethyl] steroid 8. It proved possible to hydrolyze these compounds under relatively mild conditions to 20-ketosteroids 7a,b,c and 10, showing for the first time that geminal N- and P-substituted carbon compounds do react as N,P-acetals.

  DOI：

  10.1021/jo00034a012
• 作为产物：
  描述：

  3-甲氧基雄甾-3,5-二烯-17-酮 在 potassium tert-butylate 、 二异丙胺 、 三氯氧磷 作用下， 以 四氢呋喃 为溶剂， 反应 2.17h， 生成 (E)-17-<(Diethylphosphono)isocyanomethylene>-3-methoxyandrosta-3,5-diene
  参考文献：
  名称：

  Chemistry of N,P-acetals: application to the synthesis of 20-ketosteroids

  摘要：

  A series of new derivatives of alpha-(isocyanomethyl)phosphonates (6a,b,c and 9) is described, which are formed by methylation of (E)-17-[(diethylphosphono)isocyanomethylene] steroids 5a,b,c and 17-beta-[(diethylphosphono)isocyanomethyl] steroid 8. It proved possible to hydrolyze these compounds under relatively mild conditions to 20-ketosteroids 7a,b,c and 10, showing for the first time that geminal N- and P-substituted carbon compounds do react as N,P-acetals.

  DOI：

  10.1021/jo00034a012

文献信息

• Introduction of 20-keto side chains in 17-oxosteroids: Wittig-Horner-Emmons reactions of (E)-17-[(diethylphosphino)isocyanomethylene]-3-methoxyandrosta-3,5-diene
  作者：Johannes Stoelwinder、Albert M. van Leusen

  DOI：10.1021/jo00066a021

  日期：1993.7

  The synthesis is described of a series of polyfunctional unsaturated DELTA16,20-20-isocyanosteroids 5a-f by the Wittig-Horner-Emmons reaction of (E)-17-[(diethylphosphono)isocyanomethylene] steroid 4 with several aldehydes and with acetone. Hydrolysis of the isocyanosteroids 5a-f with dilute sulfuric acid gave DELTA16-20-ketosteroids 6a-f in high yield. Hydrolysis of 5a was also possible under neutral conditions, via the intermediate DELTA16-20-20-isocyanatosteroid 7a, leading to A-ring protected 16-dehydroprogesterone 8a. The Wittig-Horner-Emmons reaction, together with the described hydrolyses, provides a new method for the introduction of steroid side chains. The method is particularly suited for side chains of different size, structure, and functionality.