(22S)-cholest-5-ene-3β,22-diol 3,22-diacetate | 17955-05-4

• 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: (22S)-cholest-5-ene-3β,22-diol 3,22-diacetate
• 英文别名: (22S)-3β,22-Diacetoxy-5-cholestene；(22S)-3β,22-diacetoxycholest-5-ene；(22S)-22-hydroxycholesterol diacetate；3β,22α_F-diacetoxy-cholest-5-ene；3β,22α_F-Diacetoxy-cholest-5-en；[(3S,8S,9S,10R,13S,14S,17R)-17-[(2S,3S)-3-acetyloxy-6-methylheptan-2-yl]-10,13-dimethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-yl] acetate
• CAS: 17955-05-4
• 化学式: C₃₁H₅₀O₄
• 分子量: 486.736
• InChiKey: RWLPOCUZGPJTTC-AFABWVAVSA-N

物化性质

• 沸点：
  536.3±33.0 °C(predicted)
• 密度：
  1.04±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.2
• 重原子数：
  35
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (22S)-cholest-5-ene-3β,22-diol 3,22-diacetate 在 platinum on activated charcoal 氢气 作用下， 以 乙酸乙酯 为溶剂， 反应 3.0h， 以73%的产率得到Cholestane-3,22-diol, diacetate, (3b,5a,22S)-
  参考文献：
  名称：

  Stereoselective construction of 22-oxygenated steroid side chains by dimethylaluminum chloride-mediated ene reactions of aldehydes

  摘要：

  Dimethylaluminum chloride-mediated ene reactions of aldehydes with (Z)-3beta-acetoxy-5,17(20)-pregnadiene (3) at low temperatures followed by acetylation of the resulting alcohols have been shown to produce stereoselectively 22-acetoxylated steroid derivatives in good to excellent yields. Interestingly, the stereochemical outcome of these ene reactions has been found to be dependent upon the size of the aldehyde employed; the less sterically demanding aldehydes such as 4-methylpentanal and cyclohexanecarboxaldehyde afford the (20alpha,22alpha)-22-acetoxy products (4a) stereoselectively, whereas the relatively congested aldehydes such as benzaldehyde and other aromatic aldehydes produce predominantly the (20alpha,22beta)-22-acetates (4b). This novel stereochemical observation has been rationalized in terms of the relative stabilities of the two most plausible transition states where the difference in the relative bulk between the R group of the aldehyde RCHO and the Me2AlCl coordinating to the aldehyde oxygen in an anti-fashion seems to be manifested in the stereochemical outcome at C-22 of the ene products.

  DOI：

  10.1021/jo00068a024
• 作为产物：
  描述：

  去氢表雄酮 在 platinum on activated charcoal 吡啶 、 potassium tert-butylate 、 氢气 、 二甲基氯化铝 作用下， 以 乙醚 、 乙醇 、 二氯甲烷 、 氯仿 、 甲苯 为溶剂， 反应 39.0h， 生成 (22S)-cholest-5-ene-3β,22-diol 3,22-diacetate
  参考文献：
  名称：

  Stereoselective construction of 22-oxygenated steroid side chains by dimethylaluminum chloride-mediated ene reactions of aldehydes

  摘要：

  Dimethylaluminum chloride-mediated ene reactions of aldehydes with (Z)-3beta-acetoxy-5,17(20)-pregnadiene (3) at low temperatures followed by acetylation of the resulting alcohols have been shown to produce stereoselectively 22-acetoxylated steroid derivatives in good to excellent yields. Interestingly, the stereochemical outcome of these ene reactions has been found to be dependent upon the size of the aldehyde employed; the less sterically demanding aldehydes such as 4-methylpentanal and cyclohexanecarboxaldehyde afford the (20alpha,22alpha)-22-acetoxy products (4a) stereoselectively, whereas the relatively congested aldehydes such as benzaldehyde and other aromatic aldehydes produce predominantly the (20alpha,22beta)-22-acetates (4b). This novel stereochemical observation has been rationalized in terms of the relative stabilities of the two most plausible transition states where the difference in the relative bulk between the R group of the aldehyde RCHO and the Me2AlCl coordinating to the aldehyde oxygen in an anti-fashion seems to be manifested in the stereochemical outcome at C-22 of the ene products.

  DOI：

  10.1021/jo00068a024

文献信息

• Stereoselective synthesis of plant growth-prompting steroids, brassinolide, castasterone, typhasterol, and their 28-nor analogues
  作者：Suguru Takatsuto、Naoto Yazawa、Masaji Ishiguro、Masuo Morisaki、Nobuo Ikekawa

  DOI：10.1039/p19840000139

  日期：——

  Plant growth-promoting steroids, brassinolide (1a), (22R,23R,24S)-2α,3α,22,23-tetrahydroxy-B-homo-7-oxa-5α-ergostan-6-one, castasterone (2a), (22R,23R,24S)-2α,3α,22,23-tetrahydroxy-5α-ergo-stan-6-one, 28-norbrassinolide (1b), (22R,23R)-2α,3α,22,23-tetrahydroxy-B-homo-7-oxa-5α-chole-stan-6-one, brassinone (2b), (22R,23R)-2α,3α,22,23-tetrahydroxy-5α-cholestan-6-one, and typh-asterol (2c), (22R,23R,24S)-3α

  促进植物生长的类固醇，油菜素内酯（1a），（22 R，23 R，24 S）-2α，3α，22,23-四羟基-B -homo-7-oxa-5α-ergostan-6-one，卡司他酮（ 2a），（22 R，23 R，24 S）-2α，3α，22,23-四羟基-5α-麦角甾烷-6-一，28-去甲油菜素内酯（1b），（22 R，23 R）-2α ，3α，22,23-tetrahydroxy- B -homo-7-oxa-5α-hole-stan-6-，brasinone（2b），（22 R，23 R）-2α，3α，22,23-tetrahydroxy- 5α-胆甾醇-6-1和伤寒甾醇（2c），（22 R，23 R，24 S）-3α，22,23-三羟基-5α.-麦角甾醇-6-，已被立体选择性地合成。这些类固醇在三种不同的生物测定法中显示出非常强的生物学活性。
• Stereochemistry of hydroboration of .alpha.-chiral olefins and reduction of .alpha.-chiral ketones. An unusual anti-Cram selectivity with dialkylboranes
  作者：M. Mark Midland、Young C. Kwon

  DOI：10.1021/ja00349a071

  日期：1983.6

  An 4 Modellverbindungen, dem Steroid (I) (keine nahere Angabe), dem Pregnenolon (IV), dessen Wittig- Produkt (VII) unddem Butanon (IX) wird der Einflus von Reduktionsmitteln auf die Stereochemie der Reduktion untersucht.

  An 4 Modellverbindungen, dem Steroid (I) (keine nahere Angabe), dem Pregnenolon (IV), dessen Wittig-Produkt (VII) unddem Butanon (IX) wird der Einflus von Reduktionsmitteln auf die Stereochemie der Reduktion unterochemie
• Stereospecific synthesis of the side chain of the steroidal plant sex hormone oogoniol
  作者：James R. Wiersig、Nada Waespe-Sarcevic、Carl Djerassi

  DOI：10.1021/jo01333a021

  日期：1979.9
• Anastasia, Mario; Ciuffreda, Pierangela; Puppo, Marina Del, Journal of the Chemical Society. Perkin transactions I, 1983, # 2, p. 383 - 386
  作者：Anastasia, Mario、Ciuffreda, Pierangela、Puppo, Marina Del、Fiecchi, Alberto

  DOI：——

  日期：——
• Synthesis of (20R,25R)-cholest-5-ene-3.beta.,26-diol and the occurrence of base-catalyzed 1,5-hydride shift in a steroidal 1,5-ketol
  作者：Arthur F. Kluge、Michael L. Maddox、Leslie G. Partridge

  DOI：10.1021/jo00213a031

  日期：1985.6