(+/-)-16-hydroxy-3-methoxy-14β-methylgona-1,3,5(10),9,16-pentaen-15-one | 135586-90-2

• 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: (+/-)-16-hydroxy-3-methoxy-14β-methylgona-1,3,5(10),9,16-pentaen-15-one
• 英文别名: (8S,13S,14R)-16-hydroxy-3-methoxy-14-methyl-7,8,12,13-tetrahydro-6H-cyclopenta[a]phenanthren-15-one
• CAS: 135586-90-2
• 化学式: C₁₉H₂₀O₃
• 分子量: 296.366
• InChiKey: IKBYLLWEWPNCGB-XGINMYPSSA-N

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：
  0.42
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  7-甲氧基-4-乙烯基-1,2-二氢萘 、 1-Methylcyclopent-1-en-3,4-dione 以 1,4-二氧六环 为溶剂， 反应 50.0h， 生成 (+/-)-16-hydroxy-3-methoxy-14β-methylgona-1,3,5(10),9,16-pentaen-15-one
  参考文献：
  名称：

  在具有雌激素或18a-同型雌激素骨架的类固醇上证实了具有生色开口动作的全合成† ‡ §

  摘要：

  Dane在1930年代后期提出了合成标题化合物的首选方法。很快就被拒绝了，因为开场动作–致色Diels - Alder反应–无效。但是，以路易斯酸为介质，现在已经取得了成功的开始。使用螯合配体的Ti络合物（Seebach 's TADDOLs（=α，α，α'，α'-四芳基-1,3-二氧戊环-4,5-二甲醇）），确实发生了所需加合物的对映选择性形成。已经完成了2和3a的有效总合成。

  DOI：

  10.1002/hlca.19950780524

文献信息

• Enantioselective Synthesis of (+)-Estrone Exploiting a Hydrogen Bond-Promoted Diels−Alder Reaction
  作者：Marko Weimar、Gerd Dürner、Jan W. Bats、Michael W. Göbel

  DOI：10.1021/jo100053j

  日期：2010.4.16

  Starting from Dane’s diene and methylcyclopentenedione, (+)-estrone is synthesized along the Quinkert−Dane route in 24% total yield. The key step is an enantioselective Diels−Alder reaction promoted by an amidinium catalyst as efficiently as by a traditional Ti-TADDOLate Lewis acid.

  从 Dane 的二烯和甲基环戊烯二酮开始，沿 Quinkert-Dane 路线合成 (+)-雌酮，总产率为 24%。关键步骤是由脒催化剂与传统的 Ti-TADDOLate Lewis 酸一样有效地促进对映选择性 Diels-Alder 反应。
• Catalysis of a Diels−Alder Reaction by Amidinium Ions
  作者：Tilmann Schuster、Markus Kurz、Michael W. Göbel

  DOI：10.1021/jo991372x

  日期：2000.3.1

  lipophilic amidinium ions catalyze a cycloaddition reaction representing the key step of the Quinkert-Dane estrone synthesis. Hydrogen-bond-mediated association with the organic cation leads to an electrophilic activation of the dienophile and to enhanced rates of the Diels-Alder reaction. The observed effects are similar to those expected from mild Lewis acids. In competition experiments, amidinium catalysis

  molecular和胍是分子识别和客体化学中重要的官能团。此处显示亲脂性am离子可催化环加成反应，该反应代表了Quinkert-Dane雌酮合成的关键步骤。氢键介导的与有机阳离子的缔合导致亲二烯体的亲电子活化并提高了狄尔斯-阿尔德反应的速率。观察到的效果与温和的路易斯酸所预期的效果相似。在竞争实验中，idi催化促进了电子缺乏程度较低的亲双烯体的反应。
• A C2-Chiral Bis(amidinium) Catalyst for a Diels−Alder Reaction Constituting the Key Step of the Quinkert−Dane Estrone Synthesis
  作者：Svetlana B. Tsogoeva、Gerd Dürner、Michael Bolte、Michael W. Göbel

  DOI：10.1002/ejoc.200200635

  日期：2003.5

  A novel C2-chiral bis(amidinium) salt 12 has been synthesised from 5-(tert-butyl)isophthalic acid. The hydrogen-bond-mediated association of dienophiles 3a and 3b with the chiral host molecule 12 accelerates the Diels−Alder reactions with diene 2 by more than three orders of magnitude. In addition, enantioselective formation of the desired adducts is observed under catalysis with 12. Good ratios of

  一种新型 C2-手性双 (脒) 盐 12 已由 5-(叔丁基) 间苯二甲酸合成。氢键介导的亲二烯体 3a 和 3b 与手性主体分子 12 的结合加速了与二烯 2 的 Diels-Alder 反应三个数量级以上。此外，在 12 的催化下观察到所需加合物的对映选择性形成。 4a(b) + ent-4a(b)/5a(b) + ent-5a(b) 的良好比例为 1:10 至 1:22在所有反应中都发现了。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
• E. Dane's route to estrone revisited
  作者：Gerhard Quinkert、Michael del Grosso、Astrid Bucher、Jan W. Bats、Gerd Dürner

  DOI：10.1016/s0040-4039(00)92705-9

  日期：1991.7

  The chirogenic Diels/Alder reactions of the general pattern AB + D --> ABCD, (i): 2 + 3 --> rac-8a (major) + rac-9a (minor) (85%), (ii): 2 + 10a --> rac-11a (89%), and (iii): 2 + 10b --> rac-11b (90%), now have been accomplished in the presence of Lewis acid, (i): BF3.OEt2, (ii) or (iii): TiCl4. Case (iii) may be used as the initial move towards (+/-)-norgestrel (rac-14).
• Axially Chiral Amidinium Ions as Inducers of Enantioselectivity in Diels−Alder Reactions
  作者：Tilmann Schuster、Markus Bauch、Gerd Dürner、Michael W. Göbel

  DOI：10.1021/ol991276i

  日期：2000.1.1

  Enantioselective catalysis of Diels-Alder reactions is mostly achieved by coordinating the dienophile to relatively strong chiral Lewis acids. Here we report on a novel approach employing the hydrogen bond mediated association of dienophiles to chiral host molecules, In a reaction forming the steroid skeleton of norgestrel, chiral amidinium ions induce 5:ent-5 ratios of up to 2,5:1. Improved and simplified amidinium catalysts may become interesting candidates to perform stereoselective transformations.