(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

• Synthesis of 10,11-didehydro- and 10,11-dihydro-Quincorine and of the Quincoridine analogs: functionalized and enantiopure 1-azabicyclo[2.2.2]-octanes with four stereogenic centers
  作者：Olaf Schrake、Wilfried Braje、H.M.R. Hoffmann、R. Wartchow

  DOI：10.1016/s0957-4166(98)00364-4

  日期：1998.10

  The convenient synthesis of 10,11-didehydro-QCI (2) and of 10,11-didehydro-QCD (4) as well as 10,11-dihydro-QCI (5) and 10,11-dihydro-QCD (6) is described. Conversion of the olefinic double bond of Quincorine®1 and Quincoridine®3 into the corresponding alkynes 2 and 4 involves twofold dehydrobromination, and an important application of the solid KOH/aliquat 336 system in the key step. The structure

  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。
• 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.
• Synthesis of Enantiopure 1-Azabicyclo[3.2.2]nonanes via Stereoselective Capture of Chiral Carbocations
  作者：Stefanie Röper、Jens Frackenpohl、Olaf Schrake、Rudolf Wartchow、H. M. R. Hoffmann

  DOI：10.1021/ol0057378

  日期：2000.6.1

  [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.