(1S,2S,4S,5S)-2-Hydroxymethyl-5-(4-nitrophenylethynyl)-1-azabicyclo[2.2.2]octane

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (1S,2S,4S,5S)-2-Hydroxymethyl-5-(4-nitrophenylethynyl)-1-azabicyclo[2.2.2]octane
• 英文别名: [(2S,4S,5S)-5-[2-(4-nitrophenyl)ethynyl]-1-azabicyclo[2.2.2]octan-2-yl]methanol
• 化学式: C₁₆H₁₈N₂O₃
• 分子量: 286.331
• InChiKey: BLFFPFQPHCTQQA-DZKIICNBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  69.3
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1S,2S,4S,5S)-2-Hydroxymethyl-5-(4-nitrophenylethynyl)-1-azabicyclo[2.2.2]octane 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,5S)-2-iodomethyl-5-(p-nitrophenylethynyl)-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 bis-triphenylphosphine-palladium(II) chloride copper(l) iodide 、 溴 、 三乙胺 作用下， 以 四氢呋喃 、 四氯化碳 、 氯仿 为溶剂， 反应 4.75h， 生成 (1S,2S,4S,5S)-2-Hydroxymethyl-5-(4-nitrophenylethynyl)-1-azabicyclo[2.2.2]octane
  参考文献：
  名称：

  Cross-coupling reactions in Cinchona alkaloid chemistry: aryl-substituted and dimeric quinine, quinidine, as well as quincorine and quincoridine derivatives

  摘要：

  改良Cincona生物碱的交叉耦合反应可以合成多种新型的芳基化和二聚体奎宁及奎尼丁衍生物，包含单一和双重的1,2-氨醇功能团。Sonogashira和Heck反应允许对乙炔和11-碘乙烯前体进行功能化。研究了旁观者功能团的作用。

  DOI：

  10.1039/b004693k

文献信息

• 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.
• Cross-coupling reactions in Cinchona alkaloid chemistry: aryl-substituted and dimeric quinine, quinidine, as well as quincorine and quincoridine derivatives
  作者：Jens Frackenpohl、Wilfried M. Braje、H. Martin R. Hoffmann

  DOI：10.1039/b004693k

  日期：——

  Cross-coupling reactions of modified Cinchona alkaloids provide access to a wide variety of novel arylated and dimeric derivatives of quinine and quinidine containing a single and double 1,2-amino alcohol functionality. Sonogashira and Heck reactions allow functionalization of ethynyl and 11-iodovinyl precursors. The role of bystander functionality is investigated.

  改良Cincona生物碱的交叉耦合反应可以合成多种新型的芳基化和二聚体奎宁及奎尼丁衍生物，包含单一和双重的1,2-氨醇功能团。Sonogashira和Heck反应允许对乙炔和11-碘乙烯前体进行功能化。研究了旁观者功能团的作用。