methyl (3R,4S,6S)-6-(hydroxymethyl)-1-azabicyclo[2.2.2]octane-3-carboxylate

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: methyl (3R,4S,6S)-6-(hydroxymethyl)-1-azabicyclo[2.2.2]octane-3-carboxylate
• 化学式: C₁₀H₁₇NO₃
• 分子量: 199.25
• InChiKey: KEAYTRQQDQHWJM-CIUDSAMLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  49.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl (3R,4S,6S)-6-(hydroxymethyl)-1-azabicyclo[2.2.2]octane-3-carboxylate 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-1-azabicyclo[2.2.2]octane-5-carboxylic acid methyl ester
  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：

  甲醇 、 (1S,2S,5S)-2-(羟甲基)-5-乙烯基奎宁环 在 potassium permanganate 、 硫酸 、 盐酸 作用下， 以 水 为溶剂， 反应 125.0h， 以53%的产率得到methyl (3R,4S,6S)-6-(hydroxymethyl)-1-azabicyclo[2.2.2]octane-3-carboxylate
  参考文献：
  名称：

  Novel Bridged Bicyclic α-Amino Acid Esters and Key Derivatives from Quincorine and Quincoridine

  摘要：

  Oxidation of Quincorine (QCl) and Quincoridine (QCD) has been investigated, giving bicyclic a-amino acids and dicarboxylic acid derivatives, which are epimerically and also enantiomerically pure. Acidic Cr(VI)-mediated oxidation (Jones oxidation) has been optimized with respect to reaction conduct and work up (addition of ethylenediamine).

  DOI：

  10.1021/ol990981o

文献信息

• Novel Bridged Bicyclic α-Amino Acid Esters and Key Derivatives from Quincorine and Quincoridine
  作者：Olaf Schrake、Volker S. Rahn、Jens Frackenpohl、Wilfried M. Braje、H. Martin R. Hoffmann

  DOI：10.1021/ol990981o

  日期：1999.11.1

  Oxidation of Quincorine (QCl) and Quincoridine (QCD) has been investigated, giving bicyclic a-amino acids and dicarboxylic acid derivatives, which are epimerically and also enantiomerically pure. Acidic Cr(VI)-mediated oxidation (Jones oxidation) has been optimized with respect to reaction conduct and work up (addition of ethylenediamine).
• 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.