(1S,3R,4R)-3-[(R)-1-hydroxyethyl]-2-azabicyclo[2.2.1]heptane | 250360-52-2

• 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: (1S,3R,4R)-3-[(R)-1-hydroxyethyl]-2-azabicyclo[2.2.1]heptane
• 英文别名: (1R)-1-[(1S,3R,4R)-2-azabicyclo[2.2.1]heptan-3-yl]ethanol
• CAS: 250360-52-2
• 化学式: C₈H₁₅NO
• 分子量: 141.213
• InChiKey: JLZSNFDYIXHRQD-NGJRWZKOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  32.3
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  光气 、 (1S,3R,4R)-3-[(R)-1-hydroxyethyl]-2-azabicyclo[2.2.1]heptane 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 0.67h， 生成 (1S,3R,4R)-2-Azabicyclo[2.2.1]heptane-3-(R)-methylmethanol N,O-carbamate
  参考文献：
  名称：

  A Theoretical and Experimental Study of the Asymmetric Addition of Dialkylzinc toN-(Diphenylphosphinoyl)benzalimine

  摘要：

  The mechanism of the enantioselective addition of diethylzinc to N(diphenylphosphinoyl)benzalimine with catalysis by bicyclic 2-azanorbornyl-3-methanols was studied by quantum chemical calculations. The mechanism proved to differ from that of the addition of diethylzinc to aldehydes and also from an earlier proposed mechanism. The results of the calculations were used to identify several factors responsible for the selectivity. The theoretical evaluation was performed in connection with an experimental study of the effects of introducing an additional stereocenter in the ligand. An efficient route to both diastereomers of new bicyclic 2-azanorbornyl-3-methanols with an additional chiral center (the secondary alcohol group) is also presented. In the best case, an enantiomeric excess of up to 97% was obtained with these new ligands.

  DOI：

  10.1002/(sici)1521-3765(19990604)5:6<1692::aid-chem1692>3.0.co;2-m
• 作为产物：
  描述：

  (1S,3R,4R)-2-[(S)-1-Phenylethylamino]-2-azabicyclo[2.2.1]heptane-3-(R)-methylmethanol 在 palladium dihydroxide 氢气 作用下， 以 乙醇 为溶剂， 20.0 ℃ 、2.03 MPa 条件下， 反应 48.0h， 生成 (1S,3R,4R)-3-[(R)-1-hydroxyethyl]-2-azabicyclo[2.2.1]heptane
  参考文献：
  名称：

  A Theoretical and Experimental Study of the Asymmetric Addition of Dialkylzinc toN-(Diphenylphosphinoyl)benzalimine

  摘要：

  The mechanism of the enantioselective addition of diethylzinc to N(diphenylphosphinoyl)benzalimine with catalysis by bicyclic 2-azanorbornyl-3-methanols was studied by quantum chemical calculations. The mechanism proved to differ from that of the addition of diethylzinc to aldehydes and also from an earlier proposed mechanism. The results of the calculations were used to identify several factors responsible for the selectivity. The theoretical evaluation was performed in connection with an experimental study of the effects of introducing an additional stereocenter in the ligand. An efficient route to both diastereomers of new bicyclic 2-azanorbornyl-3-methanols with an additional chiral center (the secondary alcohol group) is also presented. In the best case, an enantiomeric excess of up to 97% was obtained with these new ligands.

  DOI：

  10.1002/(sici)1521-3765(19990604)5:6<1692::aid-chem1692>3.0.co;2-m
• 作为试剂：
  描述：

  苯乙酮 在 [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂ potassium isopropoxide 、 (1S,3R,4R)-3-[(R)-1-hydroxyethyl]-2-azabicyclo[2.2.1]heptane 作用下， 以 异丙醇 为溶剂， 反应 0.7h， 生成 (S)-(-)-1-苯乙醇 、 (R)-(+)-1-苯基乙醇
  参考文献：
  名称：

  2-氮杂降冰片醇：非常有效的配体，用于钌催化芳族酮的不对称转移加氢

  摘要：

  制备了2-氮杂降冰片基衍生的氨基醇，并将其评估为Ru（II）催化的芳族酮的不对称转移氢化中的配体。为了提高选择性和速率，对配体的结构进行了优化。在40分钟内于94％ee中，使用0.5 mol％的催化剂还原苯乙酮。该体系还能够将多种芳族酮还原为相应的醇，同时保持高对映选择性和产率。检查了催化剂负载和反应容器中助溶剂存在的影响，并进行了线性研究。

  DOI：

  10.1021/jo991914a

文献信息

• A Theoretical and Experimental Study of the Asymmetric Addition of Dialkylzinc toN-(Diphenylphosphinoyl)benzalimine
  作者：Peter Brandt、Christian Hedberg、Klaus Lawonn、Pedro Pinho、Pher G. Andersson

  DOI：10.1002/(sici)1521-3765(19990604)5:6<1692::aid-chem1692>3.0.co;2-m

  日期：1999.6.4

  The mechanism of the enantioselective addition of diethylzinc to N(diphenylphosphinoyl)benzalimine with catalysis by bicyclic 2-azanorbornyl-3-methanols was studied by quantum chemical calculations. The mechanism proved to differ from that of the addition of diethylzinc to aldehydes and also from an earlier proposed mechanism. The results of the calculations were used to identify several factors responsible for the selectivity. The theoretical evaluation was performed in connection with an experimental study of the effects of introducing an additional stereocenter in the ligand. An efficient route to both diastereomers of new bicyclic 2-azanorbornyl-3-methanols with an additional chiral center (the secondary alcohol group) is also presented. In the best case, an enantiomeric excess of up to 97% was obtained with these new ligands.