(1S,2R,4S)-2-(hydroxymethyl)-1-azabicyclo[2.2.2]octan-5-one | 288102-67-0

• 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)-2-(hydroxymethyl)-1-azabicyclo[2.2.2]octan-5-one
• 英文别名: (4S,6R)-6-(hydroxymethyl)-1-azabicyclo[2.2.2]octan-3-one
• CAS: 288102-67-0
• 化学式: C₈H₁₃NO₂
• 分子量: 155.197
• InChiKey: SXWPWSXEZZYEMP-NKWVEPMBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.3
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  40.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1S,2R,4S)-2-(hydroxymethyl)-1-azabicyclo[2.2.2]octan-5-one 在 silver benzoate 、 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,5R)-2-methoxy-1-azabicyclo[3.2.2]nonan-6-one
  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,2R,4S)-2-(tert-butyldimethylsilyloxymethyl)-1-azabicyclo[2.2.2]octan-5-one 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 10.0h， 以97%的产率得到(1S,2R,4S)-2-(hydroxymethyl)-1-azabicyclo[2.2.2]octan-5-one
  参考文献：
  名称：

  Synthesis of Enantiopure 3-Quinuclidinone Analogues with Three Stereogenic Centers:  (1S,2R,4S)- and (1S,2S,4S)-2-(Hydroxymethyl)-1-azabicyclo[2.2.2]octan-5-one and Stereocontrol of Nucleophilic Addition to the Carbonyl Group

  摘要：

  The pseudoenantiomeric title compounds have been prepared from quincorine (QCI) and quincoridine (QCD), respectively, in enantiopure form following an efficient six-step pathway. Nucleophilic attack at the carbonyl group proceeds preferentially from the supposedly more hindered endo pi-face, giving quinuclidinols with natural configuration at C5 (up to 97%). pi-Face selectivity is highest in the QCD series with bulky O-protecting groups, involving an unprecedented 1,7-stereoinduction.

  DOI：

  10.1021/jo9919815

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.
• Synthesis of Enantiopure 3-Quinuclidinone Analogues with Three Stereogenic Centers:  <i>(1S,2R,4S)-</i> and <i>(1S,2S,4S)</i>-2-(Hydroxymethyl)-1-azabicyclo[2.2.2]octan-5-one and Stereocontrol of Nucleophilic Addition to the Carbonyl Group
  作者：Jens Frackenpohl、H. M. R. Hoffmann

  DOI：10.1021/jo9919815

  日期：2000.6.1

  The pseudoenantiomeric title compounds have been prepared from quincorine (QCI) and quincoridine (QCD), respectively, in enantiopure form following an efficient six-step pathway. Nucleophilic attack at the carbonyl group proceeds preferentially from the supposedly more hindered endo pi-face, giving quinuclidinols with natural configuration at C5 (up to 97%). pi-Face selectivity is highest in the QCD series with bulky O-protecting groups, involving an unprecedented 1,7-stereoinduction.