(1S,3R,4S,8R,9R)-6'-methoxy-9-mercaptocinchonan | 1197385-85-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉及其衍生物
• 英文名称: (1S,3R,4S,8R,9R)-6'-methoxy-9-mercaptocinchonan
• 英文别名: 9-mercapto-epi-quinidine；(R)-[(2R,4S,5R)-5-ethenyl-1-azabicyclo[2.2.2]octan-2-yl]-(6-methoxyquinolin-4-yl)methanethiol
• CAS: 1197385-85-5
• 化学式: C₂₀H₂₄N₂OS
• 分子量: 340.489
• InChiKey: IUMPHGDATQKPSY-AFHBHXEDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  26.4
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1S,3R,4S,8R,9R)-6'-methoxy-9-mercaptocinchonan 在 碘 、 sodium hydroxide 作用下， 以 乙醇 、 水 为溶剂， 以96%的产率得到bis((1S,3R,4S,8R,9R)-6'-methoxycinchonan-9-yl)disulfide
  参考文献：
  名称：

  New chiral thiols and C2-symmetrical disulfides of Cinchona alkaloids: ligands for the asymmetric Henry reaction catalyzed by CuII complexes

  摘要：

  Seven Cinchona alkaloids were reacted with thioacetic acid and Bu3P/diethyl diazadicarboxylate in THF at 0-25 degrees C to give the corresponding thiolacetates with complete inversion of configuration at the substitution center. The thus obtained chiral thiolesters were converted into thiols and these compounds were oxidized to the respective disulfides of C-2-symmetry. Both C-9 thioles and disulfides were tested as chiral ligands in the Cu-catalyzed asymmetric Henry reaction. When the thiol derivatives of an 8,9-like configuration were applied in the reaction of benzaldehyde and nitromethane, the obtained nitroaldol was of the same absolute configuration as the catalyst and the observed enantioselectivity was up to 83% ee. These ligands gave higher ees than the corresponding thioethers, disulfides, and thioles of 8,9-unlike configuration. The results obtained are in agreement with the proposed transition-state model involving nucleophilic attack of a deprotonated nitromethane directed preferably at one side of the O-complexed benzaldehyde. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2009.07.020
• 作为产物：
  描述：

  (1S,3R,4S,8R,9R)-6'-methoxy-9-acetylthiocinchonan 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 以93%的产率得到(1S,3R,4S,8R,9R)-6'-methoxy-9-mercaptocinchonan
  参考文献：
  名称：

  New chiral thiols and C2-symmetrical disulfides of Cinchona alkaloids: ligands for the asymmetric Henry reaction catalyzed by CuII complexes

  摘要：

  Seven Cinchona alkaloids were reacted with thioacetic acid and Bu3P/diethyl diazadicarboxylate in THF at 0-25 degrees C to give the corresponding thiolacetates with complete inversion of configuration at the substitution center. The thus obtained chiral thiolesters were converted into thiols and these compounds were oxidized to the respective disulfides of C-2-symmetry. Both C-9 thioles and disulfides were tested as chiral ligands in the Cu-catalyzed asymmetric Henry reaction. When the thiol derivatives of an 8,9-like configuration were applied in the reaction of benzaldehyde and nitromethane, the obtained nitroaldol was of the same absolute configuration as the catalyst and the observed enantioselectivity was up to 83% ee. These ligands gave higher ees than the corresponding thioethers, disulfides, and thioles of 8,9-unlike configuration. The results obtained are in agreement with the proposed transition-state model involving nucleophilic attack of a deprotonated nitromethane directed preferably at one side of the O-complexed benzaldehyde. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2009.07.020

文献信息

• New chiral thiols and C2-symmetrical disulfides of Cinchona alkaloids: ligands for the asymmetric Henry reaction catalyzed by CuII complexes
  作者：Mariola Zielińska-Błajet、Jacek Skarżewski

  DOI：10.1016/j.tetasy.2009.07.020

  日期：2009.9

  Seven Cinchona alkaloids were reacted with thioacetic acid and Bu3P/diethyl diazadicarboxylate in THF at 0-25 degrees C to give the corresponding thiolacetates with complete inversion of configuration at the substitution center. The thus obtained chiral thiolesters were converted into thiols and these compounds were oxidized to the respective disulfides of C-2-symmetry. Both C-9 thioles and disulfides were tested as chiral ligands in the Cu-catalyzed asymmetric Henry reaction. When the thiol derivatives of an 8,9-like configuration were applied in the reaction of benzaldehyde and nitromethane, the obtained nitroaldol was of the same absolute configuration as the catalyst and the observed enantioselectivity was up to 83% ee. These ligands gave higher ees than the corresponding thioethers, disulfides, and thioles of 8,9-unlike configuration. The results obtained are in agreement with the proposed transition-state model involving nucleophilic attack of a deprotonated nitromethane directed preferably at one side of the O-complexed benzaldehyde. (C) 2009 Elsevier Ltd. All rights reserved.