(20R)-3β,20,26-trihydroxy-27-norcholest-5-en-22-one | 136634-01-0

• 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: (20R)-3β,20,26-trihydroxy-27-norcholest-5-en-22-one
• 英文别名: (20R)-27-norcholest-5-en-22-one-3β,20,26-triol；(2R)-2,7-dihydroxy-2-[(3S,8S,9S,10R,13S,14S,17S)-3-hydroxy-10,13-dimethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-17-yl]heptan-3-one
• CAS: 136634-01-0
• 化学式: C₂₆H₄₂O₄
• 分子量: 418.617
• InChiKey: GKWJFGAXYCHVRE-GIEGYQJMSA-N

物化性质

• 沸点：
  589.5±30.0 °C(Predicted)
• 密度：
  1.14±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  30
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  77.8
• 氢给体数：
  3
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (20R)-3β,20,26-trihydroxy-27-norcholest-5-en-22-one 在 氢氧化钾 、 一水合肼 作用下， 以 甲醇 、 三乙二醇 为溶剂， 反应 26.5h， 生成 (20R,22S)-27-norcholest-5-ene-3β,20,22-triol
  参考文献：
  名称：

  Wolff-Kishner 还原 (20R)-3β,20, 26-trihydroxy-27-norcholest-5-en-22-one 中的 1,5-氢化物位移：合成、量子化学和核磁共振研究

  摘要：

  在 160 摄氏度下用肼和 KOH 加热 (20R)-3beta,20,26-trihydroxy-27-norcholest-5-en-22-one (1) 将类固醇完全转化为新的 (20R,22RS) 的非对映异构混合物)-27-norcholest-5-ene-3beta,20,22-triols (2)。2 的排他性形成表明 1 中 C-22 酮上预期的 Wolff-Kishner 还原为亚甲基基团通过 1,5-氢化物转移转移到 C-26 位置。在酸性条件下的所有尝试都未能从 1 产生 C-22 苯腙。然而，1 的反应与苯肼在热 KOH 中反应，得到 C-26 苯腙4 作为唯一的产物。显然，在碱性条件下，氢阴离子首先经历从 C-26 CH(2)OH 基团到 C-22 酮的分子内转移，然后苯肼捕获新形成的醛。为了检验这个假设，我们根据量子化学计算构建了计算机模拟的过渡态模型，然后将这些模型的数据与含有

  DOI：

  10.1016/s0039-128x(01)00130-1
• 作为产物：
  描述：

  3β-<(tetrahydro-2H-pyran-2-yl)oxy>-5-pregnen-20-one 在 盐酸 、 叔丁基锂 作用下， 以 乙醇 为溶剂， 反应 24.0h， 生成 (20R)-3β,20,26-trihydroxy-27-norcholest-5-en-22-one
  参考文献：
  名称：

  Novel synthesis of cholesterol analogs: condensation of pregnenolone with dihydropyran or dihydrofuran

  摘要：

  Pregnenolone 3-(2'-tetrahydropyranyl) ether (1) was condensed with 3,4-[H-2]dihydropyran to mainly give (20R)-[6'-(3',4'-[2'H]dihydropyranyl)]-pregn-5-ene-3-beta,20-diol 3-(2'-tetrahydropyranyl) ether (20R-3), according to nuclear magnetic resonance (NMR). Cold, dilute HCl in ethanol removed the tetrahydropyranyl group at C-3 and also opened the dihydropyranyl ring at the C-20 position of 20R-3 to give (20R)-27-norcholest-5-en-22-one-3-beta,20,26-triol (20R-5). Analogous results were obtained by condensing pregnenolone 3-acetate with 3,4-[H-2]dihydropyran to provide (20R)-[6'-(3',4'-[2'H]dihydropyranyl)]-pregn-5-ene-3-beta,20-diol 3-acetate (20R-4). Acid-catalyzed opening of the dihydropyranyl ring at C-20 in 20R-4 yielded 20R-7, which, on acetylation followed by crystallization, provided (20R)-27-norcholest-5-en-22-one-3-beta,20,26-triol 3,26-diacetate (20R-8), identical to the diacetate made from 20R-5. Varying the reaction sequence beginning with 20(R,S)-4 gave an 84:16 ratio of 20R to 20S in a mixture of 20(R,S)-8, according to NMR analysis. Crystallization of the mixture from methanol provided pure 20R-8. Condensing 2,3-dihydrofuran and 1 for producing (20R)-[5'-(2',3'-dihydrofuranyl)]-pregn-5-ene-3-beta,20-diol 3-(2'-tetrahydropyranyl) ether (6) gave instead (20R)-26,27-bisnorcholest-5-en-22-one-3-beta,20,25-triol 3-(2'-tetrahydropyranyl) ether (20R-9) by partial hydrolysis during workup. Treating 20R-9 briefly with dilute HCl produced (20R)-26,27-bisnorcholest-5-en-22-one-3-beta,20,25-triol (20R-10). Structural assignments for the new steroids are supported by NMR, mass spectroscopy, elemental analysis, and cleavage with HIO4 of the alpha-hydroxy ketone group (at C-20 and C-22) in 5, 7, 8, 9, and 10 to give pregenolone (or pregnenolone 3-acetate). Efficient condensation of pregnenolone with 3,4-[H-2]dihydropyran or 2,3-dihydrofuran provides a novel route to elaborating the side chain on the D ring, pointing the way to new syntheses of cholesterol analogs.

  DOI：

  10.1016/0039-128x(91)90001-c