3-甲氧基-17alpha-甲基雌甾-1,3,5(10)三烯-17beta-醇 | 15236-73-4

• 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
• 中文名称: 3-甲氧基-17alpha-甲基雌甾-1,3,5(10)三烯-17beta-醇
• 英文名称: (8R,9S,13S,14S,17S)-3-methoxy-13,17-dimethyl-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenanthren-17-ol
• 英文别名: 3-Methoxy-17α-methyl-Δ^1.3.5(10)-oestratrien-17β-ol；(8R,9S,13S,14S,17S)-3-methoxy-13,17-dimethyl-7,8,9,11,12,14,15,16-octahydro-6H-cyclopenta[a]phenanthren-17-ol
• CAS: 15236-73-4
• 化学式: C₂₀H₂₈O₂
• 分子量: 300.441
• InChiKey: AZQAIRJYCUWZPD-SLHNCBLASA-N

物化性质

• 溶解度：
  溶于氯仿、DCM、

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  22
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-甲氧基-17alpha-甲基雌甾-1,3,5(10)三烯-17beta-醇 在 吡啶盐酸盐 作用下， 生成 7,15,16,17-tetrahydro-17,17-dimethyl-6H-cyclopenta[a]phenanthren-3-ol
  参考文献：
  名称：

  Potential hypolipidemic agents derived from 3-hydroxy-17,17-dimethylgona-1,3,5(10),8,11,13-hexaene

  摘要：

  Numerous aryloxy derivatives containing a lipophilic group have been found to possess hypolipidemic activity. This has prompted the preparation of various derivatives of 3-hydroxy-17,17-dimethylgona-1,3,5(10),8,11,13-hexaene (6a). In 6a the lipophilic biphenyl group is incorporated into the steroid nucleus. A three-step synthesis of 6a from 17beta-methylestradiol methyl ether was developed. The derivatives prepared were tested in rats made hypercholesterolemic with propylthiouracil. Several were found active in this test.

  DOI：

  10.1021/jm00212a008
• 作为产物：
  描述：

  雌酚酮 在 potassium hydroxide 作用下， 以 四氢呋喃 、 乙醚 、 二甲基亚砜 为溶剂， 反应 3.0h， 生成 3-甲氧基-17alpha-甲基雌甾-1,3,5(10)三烯-17beta-醇
  参考文献：
  名称：

  可控制的分子内未激活的C（sp3）-H氨基化和氨基甲酸酯的氧合

  摘要：

  双重控制的分子内未活化的C（sp 3）-H氨基化和氨基甲酸酯的氧合将可见光光催化和地球过渡金属催化结合在一起的报道。有用的氨基醇和二醇衍生物可以从容易获得的叔醇衍生物中选择性地获得。已经通过1，5-HAT方法，接着路易斯酸控制的环化，提出了可能的机理。镍和锌催化剂分别抑制氧合和胺化产物的形成。还观察到有趣的手性转移现象。

  DOI：

  10.1021/acs.orglett.8b03299

文献信息

• Regiodivergent Hydroborative Ring Opening of Epoxides via Selective C–O Bond Activation
  作者：Marc Magre、Eva Paffenholz、Bholanath Maity、Luigi Cavallo、Magnus Rueping

  DOI：10.1021/jacs.0c05917

  日期：2020.8.19

  A magnesium-catalyzed regiodivergent C–O bond cleavage protocol is presented. Readily available magnesium catalysts achieve the selective hydroboration of a wide range of epoxides and oxetanes yielding secondary and tertiary alcohols in excellent yields and regioselectivities. Experimental mechanistic investigations and DFT calculations provide insight into the unexpected regiodivergence and explain

  提出了镁催化的区域发散 C-O 键裂解方案。容易获得的镁催化剂实现了多种环氧化物和氧杂环丁烷的选择性硼氢化反应，以优异的产率和区域选择性得到仲醇和叔醇。实验机理研究和 DFT 计算提供了对意外区域发散的洞察，并解释了 C-O 键活化和产物形成的不同机制。
• Oxalates as Activating Groups for Alcohols in Visible Light Photoredox Catalysis: Formation of Quaternary Centers by Redox-Neutral Fragment Coupling
  作者：Christopher C. Nawrat、Christopher R. Jamison、Yuriy Slutskyy、David W. C. MacMillan、Larry E. Overman

  DOI：10.1021/jacs.5b07678

  日期：2015.9.9

  Alkyl oxalates are new bench-stable alcohol-activating groups for radical generation under visible light photoredox conditions. Using these precursors, the first net redox-neutral coupling of tertiary and secondary alcohols with electron-deficient alkenes is achieved.

  草酸烷基酯是新型的实验室稳定的醇活化基团，用于在可见光光氧化还原条件下产生自由基。使用这些前体，实现了叔醇和仲醇与缺电子烯烃的首次净氧化还原中性偶联。
• Metal-Free Etherification of Aryl Methyl Ether Derivatives by C–OMe Bond Cleavage
  作者：Xueqiang Wang、Chenchen Li、Xia Wang、Qingli Wang、Xiu-Qin Dong、Abing Duan、Wanxiang Zhao

  DOI：10.1021/acs.orglett.8b01696

  日期：2018.7.20

  A general and efficient protocol was developed for the synthesis of aryl alkyl ethers through metal-free C–OMe bond cleavage under mild reaction conditions. This process displays a wide scope of methoxyarenes and alcohols, including primary, secondary, and tertiary alcohols, as well as natural products, pharmaceuticals, and biologically active alcohols. DFT calculations and experimental results simultaneously

  为在温和的反应条件下通过无金属的C-OMe键裂解合成芳基烷基醚，开发了一种通用而有效的方案。该方法显示出广泛的甲氧基芳烃和醇，包括伯，仲和叔醇，以及天然产物，药物和生物活性醇。DFT计算和实验结果同时证实，钾离子通过与腈的结合在甲氧基的活化中起关键作用，并为S N Ar机制提供了支持。
• Direct Construction of Quaternary Carbons from Tertiary Alcohols via Photoredox-Catalyzed Fragmentation of <i>tert</i>-Alkyl <i>N</i>-Phthalimidoyl Oxalates
  作者：Gregory L. Lackner、Kyle W. Quasdorf、Larry E. Overman

  DOI：10.1021/ja408971t

  日期：2013.10.16

  A convenient method for the direct construction of quaternary carbons from tertiary alcohols by visible-light photoredox coupling of tert-alkyl N-phthalimidoyl oxalate intermediates with electron-deficient alkenes is reported.

  报道了一种通过可见光光氧化还原偶联由叔醇直接构建季碳的简便方法，N-邻苯二甲酰草酸叔烷基中间体与缺电子烯烃。
• Fragment Coupling and the Construction of Quaternary Carbons Using Tertiary Radicals Generated From<i>tert</i>-Alkyl<i>N</i>-Phthalimidoyl Oxalates By Visible-Light Photocatalysis
  作者：Gregory L. Lackner、Kyle W. Quasdorf、Gerald Pratsch、Larry E. Overman

  DOI：10.1021/acs.joc.5b00794

  日期：2015.6.19

  visible-light, catalytic Ru(bpy)3(PF6)2, and a reductant fragments to form the corresponding tertiary carbon radical. In addition to reductive coupling with alkenes, substitution reactions of tertiary radicals with allylic and vinylic halides is described. A mechanism for the generation of tertiary carbon radicals from tert-alkyl N-phthalimidoyl oxalates is proposed that is based on earlier pioneering investigations

  叔碳自由基与烯烃受体的偶联是结合复杂碳片段并形成新季碳的尚未开发的策略。描述了从叔醇生成亲核叔自由基并在片段偶联反应中利用这些中间体的新方法的范围和局限性。该方法首先将叔醇酰化，得到N-邻苯二甲酰亚氨基草酸叔烷基酯，在可见光催化下Ru(bpy)3(PF6)2和还原剂片段存在，生成相应的叔醇碳自由基。除了与烯烃的还原偶联外，还描述了叔自由基与烯丙基和乙烯基卤化物的取代反应。基于 Okada 和 Barton 的早期开创性研究，提出了一种由 N-邻苯二甲酰亚氨基草酸叔烷基酯生成叔碳自由基的机制。氘标记和竞争实验表明，N-邻苯二甲酰亚氨基草酸叔烷基酯与缺电子烯烃的还原自由基偶联是通过氢原子转移终止的。