4-(1α,5α,6α-6-Methoxy-3-methyl-3-azabicyclo<3.1.0>hex-6-yl)morpholine | 152089-72-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-(1α,5α,6α-6-Methoxy-3-methyl-3-azabicyclo<3.1.0>hex-6-yl)morpholine
• CAS: 152089-72-0
• 化学式: C₁₁H₂₀N₂O₂
• 分子量: 212.292
• InChiKey: NYQZJFQZIXNAPK-URLYPYJESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.15
• 重原子数：
  15.0
• 可旋转键数：
  2.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  24.94
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  phenylmagnesium bromide 、 4-(1α,5α,6α-6-Methoxy-3-methyl-3-azabicyclo<3.1.0>hex-6-yl)morpholine 在 四甲基乙二胺 、 硫酸 作用下， 生成 4-(1α,5α,6α-3-Methyl-6-phenyl-3-azabicyclo[3.1.0]hex-6-yl)morpholine
  参考文献：
  名称：

  Functionalized chloroenamines in aminocyclopropane synthesis - X. amino-azabicyclo[3.1.0]hexane diastereomers from chloroenamines and - organometallic compounds

  摘要：

  Morpholino-chlorotetrahydro-N-methyl-pyridine 4 reacted with Grignard reagents 5 or diorganyl-magnesium compounds 6 to give a mixture of azabicyclo[3.1.0]hexane diastereomers 10 and 11 besides the monocyclic ketones 12. The latter were obtained as the sole products from chloroenamine 4 and dimethylzinc 7a or lithium dimethylcopper 8a. Organolithium compounds 9a,c or Grignard reagents 5a-c in the presence of TMEDA transferred 4 exclusively to endo-morpholino isomers 10. exo-Amines 11 could be obtained with high stereoselectivity from 4 via the N,O-acetal 13 and by the substitution of the methoxy moiety by a Grignard reagent 5. The stereochemical result of this substitution reaction can be explained by an intermediate complexation of the pyrrolidine N-atom in 13 by the Grignard reagent 5. An N-benzyl chloroenamine 14 instead of the N-methyl compound 4 showed a different reaction behavior with methylmagnesium bromide 5a leading only to endo-amine 15 which could be used as a precursor of the parent bicyclic system 16. The configurations of the bicyclic diamines 10, 11 and 15 were determined via H-1 NMR data.

  DOI：

  10.1016/s0040-4020(01)87188-x
• 作为产物：
  描述：

  sodium methylate 、 4-(3-氯-1,2,3,6-四氢-1-甲基-4-吡啶基)-吗啉 以 甲醇 为溶剂， 反应 20.0h， 以71%的产率得到4-(1α,5α,6α-6-Methoxy-3-methyl-3-azabicyclo<3.1.0>hex-6-yl)morpholine
  参考文献：
  名称：

  Functionalized chloroenamines in aminocyclopropane synthesis - X. amino-azabicyclo[3.1.0]hexane diastereomers from chloroenamines and - organometallic compounds

  摘要：

  Morpholino-chlorotetrahydro-N-methyl-pyridine 4 reacted with Grignard reagents 5 or diorganyl-magnesium compounds 6 to give a mixture of azabicyclo[3.1.0]hexane diastereomers 10 and 11 besides the monocyclic ketones 12. The latter were obtained as the sole products from chloroenamine 4 and dimethylzinc 7a or lithium dimethylcopper 8a. Organolithium compounds 9a,c or Grignard reagents 5a-c in the presence of TMEDA transferred 4 exclusively to endo-morpholino isomers 10. exo-Amines 11 could be obtained with high stereoselectivity from 4 via the N,O-acetal 13 and by the substitution of the methoxy moiety by a Grignard reagent 5. The stereochemical result of this substitution reaction can be explained by an intermediate complexation of the pyrrolidine N-atom in 13 by the Grignard reagent 5. An N-benzyl chloroenamine 14 instead of the N-methyl compound 4 showed a different reaction behavior with methylmagnesium bromide 5a leading only to endo-amine 15 which could be used as a precursor of the parent bicyclic system 16. The configurations of the bicyclic diamines 10, 11 and 15 were determined via H-1 NMR data.

  DOI：

  10.1016/s0040-4020(01)87188-x