(8R,9S,10S)-10,11-dihydro-9,10-epoxy-6'-methoxycinchonane

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉及其衍生物
• 英文名称: (8R,9S,10S)-10,11-dihydro-9,10-epoxy-6'-methoxycinchonane
• 英文别名: (3R,4S,6S,7R,9S)-6-(6-methoxyquinolin-4-yl)-4-methyl-5-oxa-1-azatricyclo[5.4.0.03,9]undecane
• 化学式: C₂₀H₂₄N₂O₂
• 分子量: 324.423
• InChiKey: KZAKWGUOUVYLLU-VDMLWXFKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  24
• 可旋转键数：
  2
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  34.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  奎尼丁 在 磷酸 、 potassium bromide 作用下， 反应 72.0h， 以10%的产率得到(8R,9S,10S)-10,11-dihydro-9,10-epoxy-6'-methoxycinchonane
  参考文献：
  名称：

  奎尼丁合成恶唑酮及其同系物和比绍莫类似物—金鸡纳生物碱衍生的中环系统

  摘要：

  奎尼丁（1a）乙烯基的适当官能化可实现涉及C9羟基的环化作用，产生含有扭曲的1-氮杂双环-[2.2.2]辛烷骨架的新型6元，7元和8元环。TIPS-三氟甲磺酸酯介导的羟醛13a和15b环化为甲硅烷基化的三环半缩醛14和16优于分子内S N 2-途径，尤其是对于7和8元环的形成。

  DOI：

  10.1016/s0040-4020(98)00085-4

文献信息

• β-Isocupreidine–hexafluoroisopropyl acrylate method for asymmetric Baylis–Hillman reactions
  作者：Ayako Nakano、Sakie Kawahara、Saori Akamatsu、Kenji Morokuma、Mari Nakatani、Yoshiharu Iwabuchi、Keisuke Takahashi、Jun Ishihara、Susumi Hatakeyama

  DOI：10.1016/j.tet.2005.09.072

  日期：2006.1

  Key features of the β-isocupreidine (β-ICD)-catalyzed asymmetric Baylis–Hillman reaction of aldehydes with 1,1,1,3,3,3-hexafluoroisopropyl acrylate (HFIPA) are presented. In addition, an improved method using azeotropically dried β-ICD is described.

  介绍了β-异iso啶（β-ICD）催化醛与1,1,1,3,3,3-六氟丙烯酸异丙酯（HFIPA）的不对称Baylis-Hillman反应的关键特征。另外，描述了使用共沸干燥的β-ICD的改进方法。
• Reaction of quinidine acetate, epiquinidine and its acetate in superacid: formation of gem-difluoro derivatives with or without rearrangement
  作者：Sébastien Debarge、Bruno Violeau、Marie-Paule Jouannetaud、Jean-Claude Jacquesy、Alain Cousson

  DOI：10.1016/j.tet.2005.10.004

  日期：2006.1

  presence of CCl4. Under similar conditions quinidine acetate 1b and epiquinidine acetate 2b dihydrochlorides both yield 10,10-difluoro derivatives epimeric at C-3, 6 and 7, and 9c and 10b, and a rearranged difluoro derivative 8b and 11b, respectively. Epiquinidine 2a leads to the expected analogues 10a and 11a and to a ketone 9a. Formation of gem-difluoro compounds implies chloro intermediates at C-10

  在HF-SbF 5中，奎尼丁1a或它的二盐酸盐环化物以前是用通常的酸获得的。在CCl 4的存在下观察到类似的反应。在类似条件下奎尼丁醋酸1B和epiquinidine醋酸2b的二盐酸盐产率二者10,10-二氟衍生物差向异构体在C-3，6和7，以及图9C和图10B，以及重排的二氟衍生物8B和11B分别。表奎尼丁2a生成预期的类似物10a和11a并生成酮9a。宝石-二氟化合物的形成意味着C-10处的氯中间体，即α-氯碳鎓离子的前体，它们被氟离子捕获，并通过卤素交换引入产物中。
• Reisen, Cornelius von; Jones, Peter G.; Hoffmann, H. M. R., Chemistry - A European Journal, 1996, vol. 2, # 6, p. 673 - 679
  作者：Reisen, Cornelius von、Jones, Peter G.、Hoffmann, H. M. R.

  DOI：——

  日期：——
• Synthesis of fluorhydrins by reaction of quinidine acetate, epiquinidine, and its acetate in superacid
  作者：Vincent Chagnault、Marie-Paule Jouannetaud、Jean-Claude Jacquesy、Jérome Marrot

  DOI：10.1016/j.tet.2006.07.083

  日期：2006.10

  In HF-SbF5, with or without H2O2, a source of 'OH+ equivalent, quinidine la yields three ethers, the preferred conformation of the substrate favoring the observed cyclization. Under similar conditions, quinidine acetate 1b, epiquinidine 2a, and its acetate 2b give fluorhydrins with or without rearrangement in different amounts according to the nature of the substrate and the acidity. At low acidity, epiquinidine 2a yields selectively a sole nonrearranged fluorhydrin 10a. Quinidine acetate 1b, at high acidity, yields only rearranged fluorhydrins 8b and 9b. (c) 2006 Elsevier Ltd. All rights reserved.
• Synthesis of oxazatwistanes and their homo- and bishomo-analogues from quinidine — Medium ring systems derived from cinchona alkaloids
  作者：Wilfried Braje、Jens Frackenpohl、Peter Langer、H.M.R. Hoffmann

  DOI：10.1016/s0040-4020(98)00085-4

  日期：1998.4

  involving the C9 hydroxyl group, giving novel 6-, 7- and 8-membered rings containing a distorted 1-azabicyclo-[2.2.2]octane framework. TIPS-triflate mediated cyclization of hydroxyaldehydes 13a and 15b to silylated tricyclic hemiacetals 14 and 16 is superior to an intramolecular SN2-approach, especially for the formation of 7- and 8-membered rings.

  奎尼丁（1a）乙烯基的适当官能化可实现涉及C9羟基的环化作用，产生含有扭曲的1-氮杂双环-[2.2.2]辛烷骨架的新型6元，7元和8元环。TIPS-三氟甲磺酸酯介导的羟醛13a和15b环化为甲硅烷基化的三环半缩醛14和16优于分子内S N 2-途径，尤其是对于7和8元环的形成。