(2S,3R)-2-(N,N-dimethylcarboxamido)-3-methoxycarbonylbicyclo[2.2.1]hept-5-ene | 861958-61-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (2S,3R)-2-(N,N-dimethylcarboxamido)-3-methoxycarbonylbicyclo[2.2.1]hept-5-ene
• 英文别名: (2R,3S)-methyl 3-(dimethylcarbamoyl)bicyclo[2.2.1]hept-5-ene-2-carboxylate
• CAS: 861958-61-4
• 化学式: C₁₂H₁₇NO₃
• 分子量: 223.272
• InChiKey: JZKNFSYXDBHGCO-QCLAVDOMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.69
• 重原子数：
  16.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  46.61
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (2S,3R)-2-(N,N-dimethylcarboxamido)-3-methoxycarbonylbicyclo[2.2.1]hept-5-ene 在 lithium aluminium tetrahydride 、 magnesium 作用下， 以 乙醚 为溶剂， 反应 5.0h， 生成 (2S,3R)-2-(dimethylaminomethyl)-3-(diphenylhydroxymethyl)-bicyclo[2.2.1]hept-5-ene
  参考文献：
  名称：

  Asymmetric synthesis of 1,4-amino alcohol ligands with a norbornene backbone for use in the asymmetric diethylzinc addition to benzaldehyde

  摘要：

  The asymmetric synthesis of cis-1,4-amino alcohols with a norbornene backbone was performed starting with (2S,3R)(-)-cis-hemiester 2 (98% ee). Chemoselective amination with NH4OH and HMPTA followed by LAH reduction afforded 5 and 7. respectively. Amido ester 6 was transformed into chiral ligand 9 with Grignard reaction followed by LAH reduction. The chiral ligands 5. 7. and 9 were subjected to asymmetric diethylzinc addition to examine their effectiveness as chiral catalysts. Among these, c chiral ligand 7 exhibited the highest enantioselectivity (88% ee). (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2005.04.019
• 作为产物：
  描述：

  3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride 在 奎宁 作用下， 以 四氯化碳 、 甲苯 、 苯 为溶剂， 反应 62.0h， 生成 (2S,3R)-2-(N,N-dimethylcarboxamido)-3-methoxycarbonylbicyclo[2.2.1]hept-5-ene
  参考文献：
  名称：

  Asymmetric synthesis of 1,4-amino alcohol ligands with a norbornene backbone for use in the asymmetric diethylzinc addition to benzaldehyde

  摘要：

  The asymmetric synthesis of cis-1,4-amino alcohols with a norbornene backbone was performed starting with (2S,3R)(-)-cis-hemiester 2 (98% ee). Chemoselective amination with NH4OH and HMPTA followed by LAH reduction afforded 5 and 7. respectively. Amido ester 6 was transformed into chiral ligand 9 with Grignard reaction followed by LAH reduction. The chiral ligands 5. 7. and 9 were subjected to asymmetric diethylzinc addition to examine their effectiveness as chiral catalysts. Among these, c chiral ligand 7 exhibited the highest enantioselectivity (88% ee). (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2005.04.019

文献信息

• Asymmetric synthesis of novel 1,4-aminoalcohol ligands with norbornene and norbornane backbone: use in the asymmetric diethylzinc addition to benzaldehyde
  作者：Cihangir Tanyeli、Serhat Odabaş、Mine Erdem、Esen Çakır、Eda Keskin

  DOI：10.1016/j.tetasy.2007.09.019

  日期：2007.9

  The asymmetric synthesis of cis-1,4-aminoalcohols with norbornene and norbornane backbone was performed starting with (2S, 3R)-(-)-cis-hemiester 1 (98% ee). Chemoselective amination with HMPTA followed by Grignard reactions and subsequent LAH reductions afforded compounds 5a-d. cis-Hemiester 1 was also transformed into chiral ligands 7a-f and 9a-d with the DCC coupling method followed by LAH reduction using acyclic, heterocyclic amines and various aniline derivatives and p-toluenesulfonamide, respectively. The chiral ligands were subjected to asymmetric diethylzinc addition to examine their effectiveness as chiral catalysts. Among these, arylamine and tosyl substituted chiral ligands 9a-d exhibited the highest selectivities (up to 97% ee). (c) 2007 Elsevier Ltd. All rights reserved.