3β-hydroxy-5α-cholestan-7-one | 7591-17-5

• 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-hydroxy-5α-cholestan-7-one
• 英文别名: 7-Keto-5alpha-cholestan-3beta-ol；(3S,5R,8R,9S,10S,13R,14S,17R)-3-hydroxy-10,13-dimethyl-17-[(2R)-6-methylheptan-2-yl]-1,2,3,4,5,6,8,9,11,12,14,15,16,17-tetradecahydrocyclopenta[a]phenanthren-7-one
• CAS: 7591-17-5
• 化学式: C₂₇H₄₆O₂
• 分子量: 402.661
• InChiKey: QIHXSWPLWOYYST-WIQRBZPFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.7
• 重原子数：
  29
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.96
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3β-hydroxy-5α-cholestan-7-one 在 吡啶 、 sodium tert-pentoxide 作用下， 以 乙醚 、 甲苯 为溶剂， 反应 18.19h， 生成 (5α,7α)-7-methylcholest-2-en-7-ol
  参考文献：
  名称：

  Chemical Consequences of Long-Range Orbital Interactions in Cholestane-3,7-diol Monosulfonate Esters. A Seven-Center Fragmentation

  摘要：

  The manifestation of through-five-bond interactions in the reactions of the rigid 1,5-diol monosulfonate esters (1-3), having an ideal all-trans geometry of the sigma-relay, with sodium tert-amylate is investigated. It has been shown that the deprotonation of the alcohol group in 2 and 3, which results in an increased electrofugal ability of this group, finds expression in a seven-center fragmentation. This fragmentation also illustrates that effective through-five-bond interactions exist between the alcoholate group and the carbocationic center which is generated during the heterolysis. The reaction outcome of mesylate 1 does not indicate effective through-bond interactions, and only elimination is observed. This difference can be attributed to the alkyl substituents on the gamma- and alpha-positions to the mesylate group in 2 and 3, respectively, which stimulate the seven-center fragmentation. Though a reasonable amount of fragmentation product is obtained from 3, the through-five-bond interaction is not strong enough to dominate the reaction course completely and typical El-like processes, i.e., elimination and rearrangement, are competitive. As expected, only a 1,2 Me-shift is observed in the reaction of the axial mesylate 4 where a gauche interaction is present in the geometry of the sigma-relay. The presence of through-bond interactions in the reactions of 3 and 4 becomes apparent by comparison of the reactivity of 3 and 4 with their O-silylated analogs 5 and 6.

  DOI：

  10.1021/jo951655z
• 作为产物：
  描述：

  6β-Brom-3-acetoxy-cholestanon-(7) 在 lithium aluminium tetrahydride 、 乙醚 、 potassium tert-butylate 、 叔丁醇 作用下， 生成 3β-hydroxy-5α-cholestan-7-one
  参考文献：
  名称：

  923.立体化学的各个方面。第六部分 一些环氧类固醇与三氟化硼-醚配合物的反应

  摘要：

  DOI：

  10.1039/jr9570004596

文献信息

• Regio- and Stereospecific Synthesis of Cholesterol Derivatives and Their Hormonal Activity inCaenorhabditis elegans
  作者：Arndt W. Schmidt、Thomas Doert、Sigrid Goutal、Margit Gruner、Fanny Mende、Teymuras V. Kurzchalia、Hans-Joachim Knölker

  DOI：10.1002/ejoc.200600394

  日期：2006.8

  identified. Herein, we describe the regio- and stereospecific synthesis of a number of cholesterol derivatives. The lithium–ammonia reduction of 4-cholesten-3-one was utilized to develop a general method for the introduction of diverse functional groups at C-4α of 5α-cholestan-3β-ol. Stereoselective functionalization at C-7 was achieved starting from 7-ketocholesterol derivatives. 6-Keto-5α-cholestan-3β-ol

  胆固醇对于线虫秀丽隐杆线虫的生存至关重要。最近的研究表明，胆固醇衍生物调节蠕虫生命周期中的两个过程：控制蜕皮和诱导特殊的非进食幼虫阶段。然而，胆固醇衍生信号分子的这些或任何其他功能的化学结构尚未确定。在此，我们描述了许多胆固醇衍生物的区域和立体特异性合成。4-cholesten-3-one 的锂-氨还原被用来开发一种通用方法，用于在 5α-cholestan-3β-ol 的 C-4α 处引入不同的官能团。C-7 的立体选择性功能化是从 7-酮胆固醇衍生物开始实现的。6-Keto-5α-cholestan-3β-ol 用于 C-6 和 C-7 的特定功能化。通过用这些化合物喂养不同遗传背景的蠕虫，研究了不同胆固醇衍生物的构效关系。我们的研究是确定线虫中激素活性与胆固醇不同位置取代关系的第一步。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
• Potassium borohydride reductions of ketones absorbed into polymer supports: stereochemical effects
  作者：Josie C. Briggs、Philip Hodge

  DOI：10.1039/c39880000310

  日期：——

  The proportions of 6α-alcohol obtained from aqueous potassium borohydride reductions of 3β-hydroxy-5α-cholestan-6-one (1) absorbed into various polymers varied from 0 to 90% depending on the polymer used and whether or not a phase transfer catalyst was added; some other ketones show similar stereochemical effects, the greatest effects probably arising when the substrates are adsorbed to the inner surfaces

  由硼氢化钾水溶液还原3β-羟基-5α-胆甾醇-6-一（1）吸收而得的6α-醇的比例在0至90％之间变化，具体取决于所用的聚合物以及是否使用相转移催化剂加入; 其他一些酮类化合物也显示出相似的立体化学效应，当底物吸附在适当聚合物的内表面上时，最大的效应可能会出现。
• Reactions of epoxides—XX
  作者：B.N. Blackett、J.M. Coxon、M.P. Hartshorn、B.L.J. Jackson、C.N. Muir

  DOI：10.1016/s0040-4020(01)82719-8

  日期：1969.1

  The BF3-catalysed rearrangements of exocyclic methylene epoxides at C-3, C-6, C-7 and C-12 give mixtures of epimeric aldehydes. These results are explained on the basis of the involvement of discrete carbonium ion intermediates in the rearrangement processes.

  BF 3催化的C-3，C-6，C-7和C-12上环外亚甲基环氧化物的重排产生差向异构醛的混合物。这些结果是基于离散碳离子中间体在重排过程中的参与而得到解释的。
• Über Steroide und Sexualhormone. 151. Mitteilung. Über die Aufspaltung des Ringes B im 7-Keto-cholestanol durch Oxydation mit Benzopersäure
  作者：H. Heusser、A. Segre、Pl. A. Plattner

  DOI：10.1002/hlca.19480310428

  日期：——

  7-Keto-cholestanol, dessen Acetat, Benzoat und Pivalat wurden durch Oxydation mit Benzopersäure in die entsprechenden (78)-Lactone (IV–IVc) übergeführt. Das 3-Oxy-(78)-lacton IV liess sich nicht zum 8-Oxy-(73)-lacton isomerisieren. Auch die Überführung des Lactons IV in das 8-Keto-(73)-lecton II gelang nicht.

  通过用苯甲酸过氧化将7-酮-胆固醇，其乙酸盐，苯甲酸酯和新戊酸酯转化为相应的（78）-内酯（IV-IVc）。3-氧-（78）-内酯IV不能异构化为8-氧-（73）-内酯。内酯IV向8-酮-（73）-lectone II的转化也没有成功。
• 7-Oxo-7a-oxa-brassinosteroids with Cholestane Side-Chain
  作者：Ladislav Kohout

  DOI：10.1135/cccc19941219

  日期：——

  New 7-oxo-7a-oxa analogs of brassinolide with cholestane side-chain were prepared. Analogs VIII and IX with 2,3-diol grouping exhibit a weak brassinolide activity. Of the synthesized compounds, the highest brassinolide activity was found for 3α,4α-dihydroxy-7a-oxa-B-homo-5α-cholestan-7-one (X).

  制备了具有胆甾烷侧链的新的7-氧杂-7a-氧杂油菜素类似物。具有2,3-二醇基团的类似物VIII和IX表现出较弱的油菜素活性。在合成的化合物中，3α，4α-二羟基-7a-氧杂-B-同型-5α-胆甾烷-7-酮（X）具有最高的油菜素活性。