4β,5β-methano-3α-cholestan-3β-ol | 13903-59-8

• 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: 4β,5β-methano-3α-cholestan-3β-ol
• 英文别名: (1S,2R,5S,6R,8S,11S,12S,15R,16R)-2,16-dimethyl-15-[(2R)-6-methylheptan-2-yl]pentacyclo[9.7.0.02,8.06,8.012,16]octadecan-5-ol
• CAS: 13903-59-8
• 化学式: C₂₈H₄₈O
• 分子量: 400.689
• InChiKey: NHCFIELJCQCTTN-HBLHVUAWSA-N

物化性质

• 沸点：
  487.0±14.0 °C(Predicted)
• 密度：
  1.01±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  9.3
• 重原子数：
  29
• 可旋转键数：
  5
• 环数：
  5.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4β,5β-methano-3α-cholestan-3β-ol 在 chromium trioxide-pyridine complex 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以91%的产率得到4β,5β-methano-5α-cholestan-3-one
  参考文献：
  名称：

  4,5-Cyclopropanocholestan-3β-ol Substrates for Cholesterol Oxidase and Their ¹H NMR Assignments

  摘要：

  We have assayed 4,5-cyclopropanocholestan-3-ols and 4,5-cyclopropanocholestan-3-ones and tested them as substrates and inhibitors of cholesterol oxidase. The 4,5-cyclopropanocholestan-3 beta-ols (alpha and beta) are substrates of cholesterol oxidase that are converted to their respective ketones 1000-fold more slowly than cholesterol. The induced ring-current effects of a cyclopropane ring are clearly illustrated in the H-1 NMR spectra of these sterols. These shielding effects are dramatic because of the rigidity of the steroid backbone. Assignments of the H-1 resonances of the A, B, and cyclopropyl rings of the sterols have been made using DQF-COSY and NOESY experiments. We have assigned the upheld multiplet at approximately 0.5 ppm to H-6 alpha in both isomers. H-6 alpha is Shielded by the cyclopropyl sigma bond. H-6 beta is deshielded by the cyclopropane ring and appears at approximately 2.0 ppm in both isomers.

  DOI：

  10.1021/jo9706537
• 作为产物：
  描述：

  4β,5-cyclopropano-5β-cholestan-3α-ol 在 jones' reagent 、 lithium tri(t-butoxy)aluminum hydride 作用下， 以 乙二醇二甲醚 、 丙酮 为溶剂， 生成 4β,5β-methano-3α-cholestan-3β-ol
  参考文献：
  名称：

  Joska, Jiri; Fajkos, Jan, Collection of Czechoslovak Chemical Communications, 1980, vol. 45, # 6, p. 1850 - 1859

  摘要：

  DOI：

文献信息

• Design, synthesis, application and recovery of a minimally fluorous diaryl diselenide for the catalysis of stannane-mediated radical chain reactions
  作者：David Crich、Xiaolin Hao、Mathew Lucas

  DOI：10.1016/s0040-4020(99)00902-3

  日期：1999.12

  diselenide is described. On reduction in situ with tributylstannane this diselenide provides a fluorous selenol which is effective in inhibiting a range of stannane-mediated radical rearrangements, including a cyclopropylcarbinyl ring opening. A method for the recovery of the fluorous diselenide involving continuous extraction in a modified, cooled continuous extractor is described.

  描述了最低氟（52％F）二芳基二硒化物的合成。在用三丁基锡烷原位还原时，该二硒化物提供了一种氟硒醇，其有效抑制了由锡烷介导的自由基重排的范围，包括环丙基羰基的开环。描述了一种回收二硒氟的方法，该方法包括在改良的冷却的连续萃取器中连续萃取。
• Inhibition of Stannane-Mediated Radical Rearrangements by a Recoverable, Minimally Fluorous Selenol
  作者：David Crich、Xiaolin Hao、Mathew A. Lucas

  DOI：10.1021/ol990590+

  日期：1999.7.1

  [GRAPHICS]The preparation of a minimally fluorous diaryl diselenide is described. It is demonstrated that this diselenide, reduced in situ to the corresponding selenol, may be used in conjunction with stannanes to prevent a number of radical rearrangements. A 1 M solution of this selenol used in admixture with Breslow's water-soluble stannane can be used to significantly inhibit a cyclopropylcarbinyl ring opening. The combination of the fluorous selenol and the polar stannane permits recovery of the selenol by continuous fluorous extraction and isolation of a stannane-free hydrocarbon product.