(2S,4S,5R)-5-乙基-2-奎宁环基甲醇 | 219794-79-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 奎宁环
• 中文名称: (2S,4S,5R)-5-乙基-2-奎宁环基甲醇
• 英文名称: (2S,4S,5R)-2-Hydroxymethyl-5-ethylquinuclidine
• 英文别名: [(2S,4S,5R)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol
• CAS: 219794-79-3
• 化学式: C₁₀H₁₉NO
• 分子量: 169.267
• InChiKey: CWZWBZXPEJJRSS-GUBZILKMSA-N

物化性质

• 沸点：
  252.6±13.0 °C(Predicted)
• 密度：
  1.04±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  23.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2S,4S,5R)-5-乙基-2-奎宁环基甲醇 在 三乙胺 、 lithium iodide 作用下， 以 1,4-二氧六环 、 二氯甲烷 为溶剂， 生成 (1S,2S,4S,5R)-2-iodomethyl-5-ethyl-1-azabicyclo[2.2.2]octane
  参考文献：
  名称：

  Synthesis of Enantiopure 1-Azabicyclo[3.2.2]nonanes via Stereoselective Capture of Chiral Carbocations

  摘要：

  [GRAPHICS]A new class of doubly functionalized and enantiomerically pure 1-azabicyclo[3.2.2]nonanes derived from quincorine and quincoridine is described. 2,5-Disubstituted quinuclidines with a C9-mesyloxy group were easily transformed into the corresponding halides upon treatment with lithium salts. Subsequent silver salt-mediated ring expansion stereoselectively furnished the title azabicyclics. Chiral carbocations which are configurationally stable and nonplanar are postulated to account for the striking stereoselectivity of the capture of external nucleophile. 5-Ethynyl-2-iodomethylquinuclidines afford the alpha-benzoyloxy amines rather than alpha-methoxy amines, even in MeOH.

  DOI：

  10.1021/ol0057378
• 作为产物：
  描述：

  (1S,2S,5S)-2-(羟甲基)-5-乙烯基奎宁环 在 Wilkinson's catalyst 、 氢气 作用下， 以 乙醇 、 甲苯 为溶剂， 反应 3.0h， 以97%的产率得到(2S,4S,5R)-5-乙基-2-奎宁环基甲醇
  参考文献：
  名称：

  合成10,11-二氢和10,11-二氢-奎宁碱和喹可啶类似物：具有四个立体生成中心的功能化和对映纯的1-氮杂双环[2.2.2]-辛烷

  摘要：

  方便合成10,11-二氢-QCI（2）和10,11-二氢-QCD（4）以及10,11-二氢-QCI（5）和10,11-二氢-QCD（6）描述。Quincorine的烯属双键的转化率® 1和Quincoridine ® 3为相应的炔烃2和4涉及双重脱溴化氢，并将固体KOH的一个重要应用/ ALIQUAT在关键步骤336系统。X射线晶体衍射已阐明了二氢-QCI（2）的结构。新炔烃2和4 分别比QCI和QCD更具极性和更基础。

  DOI：

  10.1016/s0957-4166(98)00364-4

文献信息

• Cinchona alkaloid derived ligands in catalytic asymmetric transfer hydrogenation
  作者：Antti Hartikka、Stefan A. Modin、Pher G. Andersson、Per I. Arvidsson

  DOI：10.1039/b304060g

  日期：——

  A collection of chiral quinuclidine ligands, derived from the Cinchona alkaloids quinine and quinidine, has been evaluated in the catalytic asymmetric transfer hydrogenation of aromatic ketones. It was fond that [IrCl(COD)]2 complexes of the diamines QCI-Amine and QCD-Amine gave the most active catalysts, capable of reducing a range of aromatic ketones with excellent conversions and good enantioselectivities

  衍生自金鸡纳生物碱奎宁和奎尼丁的手性奎宁环配体的集合已在芳族酮的催化不对称转移氢化中得到了评估。令人高兴的是，二胺QCI-胺和QCD-胺的[IrCl（COD）] 2络合物提供了最具活性的催化剂，能够还原一系列芳族酮，并具有出色的转化率和良好的对映选择性（最高95％ee）。这些是报道的基于喹uc啶核不对称转化的配体的最佳选择性，并提倡以假对映体形式商购的这些配体将在该催化方法和其他催化方法中得到实际应用。
• New P,N ligands with chiral nitrogen center: applications in homogeneous catalysis
  作者：Christine Saluzzo、Jérémy Breuzard、Stéphane Pellet-Rostaing、Martial Vallet、Frédéric Le Guyader、Marc Lemaire

  DOI：10.1016/s0022-328x(01)01148-2

  日期：2002.2

  In order to perform homogeneous asymmetric hydroformylation, hydrosilylation and Grignard cross-coupling reaction, we have developed a new family of RN ligands derived from quincorine and quincoridine. (C) 2002 Elsevier Science B.V. All rights reserved.
• Grignard cross-coupling catalyzed by chiral phosphino–quincorine and phosphino–quincoridine derivatives
  作者：Stéphane Pellet-Rostaing、Christine Saluzzo、Rob Ter Halle、Jérémy Breuzard、Laurent Vial、Frédéric Le Guyader、Marc Lemaire

  DOI：10.1016/s0957-4166(01)00342-1

  日期：2001.8

  New beta -aminoalkylphosphines with a stereogenic nitrogen center have been synthesized from quincorine and quincoridine. Nickel catalysts were studied for their enantioselectivity in the asymmetric Kumada-Corriu reaction. The (2S,4S,5R)-2-diphenylphosphinomethyl-5-ethyl-quinuclidine-nickel complex led to e.e. of 85%, for the cross-coupling of 1-phenylethyl-magnesium chloride with vinyl bromide. (C) 2001 Elsevier Science Ltd. All rights reserved.
• New hydrogenated and didehydrogenated 1,2-diamines of quincorine and quincoridine
  作者：Ion Neda、Thomas Kaukorat、Christian Hrib

  DOI：10.1016/s0957-4166(02)00320-8

  日期：2002.7

  Four new members of the family of 1,2-diamines of quincorine and quincoridine have been synthesized, being hydrogenated and didehydrogenated at the C10-C11 fragment. The alkynes, containing an additional amino group at C9, are potentially useful building blocks for cross-coupling reactions. Additional investigations concerning the chemical properties of the molecules point to a significant impact of the remote C5 substituent on the basicity of the bridgehead nitrogen. (C) 2002 Elsevier Science Ltd. All rights reserved.