3-methoxy-16-methylene-estra-1,3,5(10)-trien-17-one | 18011-90-0

• 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: 3-methoxy-16-methylene-estra-1,3,5(10)-trien-17-one
• 英文别名: (8R,9S,13S,14S)-3-methoxy-13-methyl-16-methylidene-6,7,8,9,11,12,14,15-octahydrocyclopenta[a]phenanthren-17-one
• CAS: 18011-90-0
• 化学式: C₂₀H₂₄O₂
• 分子量: 296.409
• InChiKey: CASXWAUWPXMGCE-XSYGEPLQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  22
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-methoxy-16-methylene-estra-1,3,5(10)-trien-17-one 在 甲醇 、 氢氧化钾 、 sodium tetrahydroborate 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 3.0h， 生成 3-methoxy-16β-(benzylaminomethyl)estra-1,3,5(10)-trien-17β-ol
  参考文献：
  名称：

  New steroid-fused P-heterocycles

  摘要：

  16(beta-Aminomethyl-17 beta-hydroxyestrone 3-methyl ether 6 and its N-propyl (17), N-benzyl (18) and N-arylmethyl derivatives (19-22) were subjected to ring closure reactions with phenylphosphonic dichloride in order to synthetize P-epimeric oxazaphosphorinanes 23a, 24-29 in which the hetero ring is condensed to ring D of the sterane skeleton. The stereostructures of the products were evaluated by H-1, C-13 and P-31 NMR spectroscopy. The geometry was optimized by utilizing the B3LYP DFT method. The NMR spectral data and the results of the ab initio calculations demonstrated that the stereostructure of the hetero ring was strongly affected by the rigid sterane framework condensed to it, and the phosphoramidate ring proved to adopt predominantly a distorted-boat conformation, regardless of the P-configuration. (c) 2007 Elsevier Inc. All rights reserved.

  DOI：

  10.1016/j.steroids.2007.02.001
• 作为产物：
  描述：

  3-甲氧基雌酮 在 聚合甲醛 、 sodium methylate 作用下， 以 吡啶 、 苯 为溶剂， 反应 28.0h， 生成 3-methoxy-16-methylene-estra-1,3,5(10)-trien-17-one
  参考文献：
  名称：

  钯催化的Mizoroki-Heck反应合成16- E -（[芳基]亚烷基）-3-甲氧基-雌酮

  摘要：

  使用钯催化的Mizoroki-Heck反应合成16 - E-亚芳基-3-甲氧基-雌酮。这种方法可以耐受各种官能团，并以14％至99％的产率得到相应的产物，这在很大程度上取决于芳基卤化物的电子特性。

  DOI：

  10.1016/j.tetlet.2017.06.002

文献信息

• Transition-Metal-Free Synthesis of Electron Rich 1,3-Dienes via Base Promoted Isomerization of Propargylic Ethers
  作者：Chunxiang Liu、Guogang Deng、Xin Li、Yiren Xu、Kaili Yu、Wen Chen、Hongbin Zhang、Xiaodong Yang

  DOI：10.1002/ejoc.201901743

  日期：2020.1.31

  An efficient and broadly applicable method for the construction of functionalized electron rich 1,3‐dienes through a base promoted isomerization reaction of propargylic ethers is presented. This process features easy handling reaction conditions, transition‐metal‐free isomerization, high isolated yields, and most of all, it could be used for late stage modification of natural products.

  提出了一种通过炔丙基醚的碱促进的异构化反应来构建官能化的富电子的1,3-二烯的有效方法。该工艺具有易于处理的反应条件，无过渡金属的异构化，高分离产率的特点，最重要的是，它可用于天然产物的后期改性。
• Photoredox-catalyzed procedure for carbamoyl radical generation: 3,4-dihydroquinolin-2-one and quinolin-2-one synthesis
  作者：Wade F. Petersen、Richard J. K. Taylor、James R. Donald

  DOI：10.1039/c7ob01274h

  日期：——

  A reductive approach for carbamoyl radical generation from N-hydroxyphthalimido oxamides under photoredox catalysis is outlined. This strategy was applied to the synthesis of 3,4-dihydroquinolin-2-ones via the intermolecular addition/cyclization of carbamoyl radicals with electron deficient olefins in a mild, redox-neutral manner. Under a general set of reaction conditions, diversely substituted 3

  概述了在光氧化还原催化下由N-羟基邻苯二甲酰亚胺基乙酰胺生成氨基甲酰基自由基的还原方法。该策略通过温和的，氧化还原中性的方式通过与缺电子的烯烃的氨基甲酰基基团的分子间加成/环化反应，应用于3,4-二氢喹啉-2-酮的合成。在一般的反应条件下，可以制备包括螺环系统在内的各种取代的3,4-二氢喹啉-2-酮。通过使用氯取代的烯烃，也可以得到芳族喹啉-2-酮。
• Chiral Spiro Phosphoramide-Catalyzed Sulfa-Michael Addition/Enantioselective Protonation of Exocyclic Enones
  作者：Yi-Pan Li、Shou-Fei Zhu、Qi-Lin Zhou

  DOI：10.1021/acs.orglett.9b03615

  日期：2019.12.6

  A highly efficient asymmetric Michael addition of thiols to exocyclic enones was achieved by using chiral spiro phosphoramide catalysts. The precisely chiral control in the protonation of the enol intermediate ensured high enantioselectivity. The reaction features high activity (yields up to 99%, turnover numbers up to 8400) and high enantioselectivity (up to 97% ee) with a broad substrate scope, and

  通过使用手性螺环磷酰胺催化剂，可以高效地将硫醇不对称地迈克尔加成到环外烯酮上。烯醇中间体的质子化中的精确手性控制确保了高对映选择性。该反应具有高活性（产率高达99％，周转数高达8400）和高对映选择性（高达97％ee），且具有广泛的底物范围，并且具有在手性硫化物的合成中广泛应用的潜力。
• A New Route to 16-Methylene-17-ketosteroids
  作者：Tamás Bakos、Irén Vincze

  DOI：10.1080/00397919208021602

  日期：1992.5

  Abstract A new, high-yield preparation of 16-methylene-17-ketosteroids by the methylenation of trimethylsilyl enol ethers is described.

  摘要 描述了通过三甲基甲硅烷基烯醇醚的亚甲基化反应制备 16-亚甲基-17-酮类固醇的一种新的、高产率的制备方法。
• Synthesis of Indole Terpenoid Mimics through a Functionality-Tolerated Eu(fod)₃-Catalyzed Conjugate Addition
  作者：Xiaochun Xiong、Deliang Zhang、Jian Li、Yu Sun、Shupeng Zhou、Ming Yang、Huawu Shao、Ang Li

  DOI：10.1002/asia.201403312

  日期：2015.4

  The chemical synthesis of indole terpenoids of structural and biological interests has attracted remarkable attention. Here we report an Eu(fod)3‐catalyzed indole conjugate addition reaction, which tolerates various acid‐sensitive functional groups. A collection of indole terpenoid mimics have been prepared from natural product‐derived α,β‐unsaturated enones on the basis of this reaction. The further

  具有结构和生物学意义的吲哚类萜的化学合成引起了人们的极大关注。在这里我们报告了Eu（fod）3催化的吲哚共轭加成反应，该反应可耐受各种酸敏感的官能团。在此反应的基础上，从天然产物衍生的α，β-不饱和烯酮制备了吲哚类萜模拟物。吲哚加合物进一步转化为更复杂的天然产物样分子也得到了证明。