(2R,3R)-3-(azepan-1-yl)-3-phenyl-1,2-propanediol

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氮杂环庚烷
• 英文名称: (2R,3R)-3-(azepan-1-yl)-3-phenyl-1,2-propanediol
• 英文别名: (2R,3R)-3-(azepan-1-yl)-3-phenylpropane-1,2-diol
• 化学式: C₁₅H₂₃NO₂
• 分子量: 249.353
• InChiKey: ZGMFQAIXDDDQHP-LSDHHAIUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  43.7
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  叔丁基二甲基氯硅烷 、 (2R,3R)-3-(azepan-1-yl)-3-phenyl-1,2-propanediol 在 咪唑 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 24.0h， 以71%的产率得到(1R,2R)-1-Azepan-1-yl-3-(tert-butyl-dimethyl-silanyloxy)-1-phenyl-propan-2-ol
  参考文献：
  名称：

  Synthesis of a Family of Fine-Tunable New Chiral Ligands for Catalytic Asymmetric Synthesis. Ligand Optimization through the Enantioselective Addition of Diethylzinc to Aldehydes

  摘要：

  A family of enantiomerically pure (LR,2R)-1-(dialkylamino)-1-phenyl-3-(R-oxy)-2-propanols (4) has been synthesized from (2S,3S)-2,3-epoxy-3-phenylpropanol (la), arising from the Sharpless epoxydation of cinnamyl alcohol, by two alternative sequences involving either the regioselective ring opening of the epoxide by a secondary amine (C-3 attack) and subsequent chemoselective protection of the primary hydroxy group or the reverse of these operations. A total of 19 different derivatives 4 have been prepared in an iterative process aimed at the optimization of their catalytic properties in the enantioselective addition of diethylzinc to benzaldehyde. In doing this, the steric bulk of the R-oxy group and the choice of the dialkylamino substituent as a nitrogen-containing six-membered ring have been identified as the key structural parameters for high catalytic activity and enantioselectivity in 4. Two optimized ligands fulfilling these structural requirements, 4d-Tr (R-oxy = trityloxy, dialkylamino = piperidino) and 4i-Tr (R-oxy = trityloxy, dialkylamino = 4-methylpiperazin-1-yl), depict a convenient activity and selectivity profile in the addition of Et-2-Zn to a structurally diverse family of aldehydes. These results show how chiral ligands based on non-natural starting materials can accommodate subtle variations of the steric/electronic characteristics key to the fine tuning of catalytic properties and thus represent a convenient alternative to ligands based on natural products.

  DOI：

  10.1021/jo9701445
• 作为产物：
  描述：

  环己亚胺 、 (2R,3S)-(3-phenyloxiran-2-yl)methanol 在 titanium(IV) isopropylate 作用下， 以 二氯甲烷 为溶剂， 反应 8.0h， 以91%的产率得到(2R,3R)-3-(azepan-1-yl)-3-phenyl-1,2-propanediol
  参考文献：
  名称：

  Synthesis of a Family of Fine-Tunable New Chiral Ligands for Catalytic Asymmetric Synthesis. Ligand Optimization through the Enantioselective Addition of Diethylzinc to Aldehydes

  摘要：

  A family of enantiomerically pure (LR,2R)-1-(dialkylamino)-1-phenyl-3-(R-oxy)-2-propanols (4) has been synthesized from (2S,3S)-2,3-epoxy-3-phenylpropanol (la), arising from the Sharpless epoxydation of cinnamyl alcohol, by two alternative sequences involving either the regioselective ring opening of the epoxide by a secondary amine (C-3 attack) and subsequent chemoselective protection of the primary hydroxy group or the reverse of these operations. A total of 19 different derivatives 4 have been prepared in an iterative process aimed at the optimization of their catalytic properties in the enantioselective addition of diethylzinc to benzaldehyde. In doing this, the steric bulk of the R-oxy group and the choice of the dialkylamino substituent as a nitrogen-containing six-membered ring have been identified as the key structural parameters for high catalytic activity and enantioselectivity in 4. Two optimized ligands fulfilling these structural requirements, 4d-Tr (R-oxy = trityloxy, dialkylamino = piperidino) and 4i-Tr (R-oxy = trityloxy, dialkylamino = 4-methylpiperazin-1-yl), depict a convenient activity and selectivity profile in the addition of Et-2-Zn to a structurally diverse family of aldehydes. These results show how chiral ligands based on non-natural starting materials can accommodate subtle variations of the steric/electronic characteristics key to the fine tuning of catalytic properties and thus represent a convenient alternative to ligands based on natural products.

  DOI：

  10.1021/jo9701445

文献信息

• Synthesis of a Family of Fine-Tunable New Chiral Ligands for Catalytic Asymmetric Synthesis. Ligand Optimization through the Enantioselective Addition of Diethylzinc to Aldehydes
  作者：Anton Vidal-Ferran、Albert Moyano、Miquel A. Pericàs、Antoni Riera

  DOI：10.1021/jo9701445

  日期：1997.7.1

  A family of enantiomerically pure (LR,2R)-1-(dialkylamino)-1-phenyl-3-(R-oxy)-2-propanols (4) has been synthesized from (2S,3S)-2,3-epoxy-3-phenylpropanol (la), arising from the Sharpless epoxydation of cinnamyl alcohol, by two alternative sequences involving either the regioselective ring opening of the epoxide by a secondary amine (C-3 attack) and subsequent chemoselective protection of the primary hydroxy group or the reverse of these operations. A total of 19 different derivatives 4 have been prepared in an iterative process aimed at the optimization of their catalytic properties in the enantioselective addition of diethylzinc to benzaldehyde. In doing this, the steric bulk of the R-oxy group and the choice of the dialkylamino substituent as a nitrogen-containing six-membered ring have been identified as the key structural parameters for high catalytic activity and enantioselectivity in 4. Two optimized ligands fulfilling these structural requirements, 4d-Tr (R-oxy = trityloxy, dialkylamino = piperidino) and 4i-Tr (R-oxy = trityloxy, dialkylamino = 4-methylpiperazin-1-yl), depict a convenient activity and selectivity profile in the addition of Et-2-Zn to a structurally diverse family of aldehydes. These results show how chiral ligands based on non-natural starting materials can accommodate subtle variations of the steric/electronic characteristics key to the fine tuning of catalytic properties and thus represent a convenient alternative to ligands based on natural products.