(1S,2R,4S,5R)-methanesulfonic acid 5-vinyl-1-azabicyclo-[2.2.2]oct-2-ylmetyl ester | 206983-98-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 奎宁环
• 英文名称: (1S,2R,4S,5R)-methanesulfonic acid 5-vinyl-1-azabicyclo-[2.2.2]oct-2-ylmetyl ester
• 英文别名: [(2R,4S,5R)-5-ethenyl-1-azabicyclo[2.2.2]octan-2-yl]methyl methanesulfonate
• CAS: 206983-98-4
• 化学式: C₁₁H₁₉NO₃S
• 分子量: 245.343
• InChiKey: DMBUJWSEIGFTRS-GARJFASQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  55
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1S,2R,4S,5R)-methanesulfonic acid 5-vinyl-1-azabicyclo-[2.2.2]oct-2-ylmetyl ester 在 lithium iodide 作用下， 以 1,4-二氧六环 、 丙酮 为溶剂， 反应 20.0h， 生成 (1S,2S,5R,6R)-2-benzoyloxy-6-vinyl-1-azabicyclo[3.2.2]nonane
  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：

  甲基磺酰氯 、 quincoridine 以 四氢呋喃 为溶剂， 反应 0.17h， 以95%的产率得到(1S,2R,4S,5R)-methanesulfonic acid 5-vinyl-1-azabicyclo-[2.2.2]oct-2-ylmetyl ester
  参考文献：
  名称：

  顽固氮和喹可替丁的碳C9处顽固性S N 2置换：1,2-氨基卤化物和甲硅烷基化物，具有刚性氮

  摘要：

  由于特殊的结构（“β-氨基效应”）和构象因素，研究了在奎宁碱（QCI）和奎宁丁（QCD）的碳C9处的S N 2反应是困难的。开发了用于替换各种碳原子和杂原子亲核试剂的高效实验程序。

  DOI：

  10.1016/s0040-4020(00)00330-6

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.
• Recalcitrant SN2 Displacements at Carbon C9 of Quincorine and Quincoridine: 1,2-Amino Halides and Mesylates with Configurationally Rigid Nitrogen
  作者：Olaf Schrake、M. Heiko Franz、R. Wartchow、H.M.R. Hoffmann

  DOI：10.1016/s0040-4020(00)00330-6

  日期：2000.6

  SN2 reactions at carbon C9 of Quincorine (QCI) and Quincoridine (QCD) were investigated and found to be difficult, due to the special structural (‘β-amino effect’) and conformational factors. Efficient experimental procedures for displacement with a variety of carbon and heteroatom nucleophiles were developed.

  由于特殊的结构（“β-氨基效应”）和构象因素，研究了在奎宁碱（QCI）和奎宁丁（QCD）的碳C9处的S N 2反应是困难的。开发了用于替换各种碳原子和杂原子亲核试剂的高效实验程序。