4-bromo-2-((E)-((1S,2S,3R,5S)-3-(hydroxymethyl)-2,6,6-trimethylbicyclo[3.1.1]heptan-2-ylimino)methyl)phenol | 1312714-86-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 4-bromo-2-((E)-((1S,2S,3R,5S)-3-(hydroxymethyl)-2,6,6-trimethylbicyclo[3.1.1]heptan-2-ylimino)methyl)phenol
• CAS: 1312714-86-5
• 化学式: C₁₈H₂₄BrNO₂
• 分子量: 366.298
• InChiKey: QVRNDJKWLCVEDV-WPNNLVLLSA-N

物化性质

• 熔点：
  59-62 °C(Solv: ethyl ether (60-29-7))
• 沸点：
  459.2±35.0 °C(Predicted)
• 密度：
  1.42±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.01
• 重原子数：
  22.0
• 可旋转键数：
  3.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  52.82
• 氢给体数：
  2.0
• 氢受体数：
  3.0

反应信息

• 作为产物：
  描述：

  (+)-α-蒎烯 在 盐酸 、 lithium aluminium tetrahydride 、 magnesium sulfate 、 对甲苯磺酸 、 potassium hydroxide 、 sodium sulfite 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 88.0h， 生成 4-bromo-2-((E)-((1S,2S,3R,5S)-3-(hydroxymethyl)-2,6,6-trimethylbicyclo[3.1.1]heptan-2-ylimino)methyl)phenol
  参考文献：
  名称：

  α-Pinene-type chiral Schiff bases as tridentate ligands in asymmetric addition reactions

  摘要：

  A group of tridentate Schiff bases derived from (+)-alpha-pinene were synthesized. The steric effects in the transition state, the importance of pi-pi stacking interactions as well as the electronic effects of aryl aldehydes according to Hammett constant values in the enantioselective addition of Et2Zn to aldehydes with the use of Schiff bases as chiral ligands are described. Also, a variety of aldehydes were cyanated using a catalyst prepared in situ from titanium tetraisopropoxide and chiral Schiff bases. The influence of a conjugated double-bond in the cyanation substrates on enantioselectivity was observed. The chemical structures of the chiral Schiff base-titanium alkoxide complexes are discussed based on their H-1 and C-13 NMR spectra. 3D models of the Zn-2-complex catalyst and Ti-complex catalyst containing alpha-pinane-type Schiff bases based on X-ray diffraction experiments are postulated. The models presented were consistent with the reported chirality of the addition product and observed ee. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2011.03.013
• 作为试剂：
  描述：

  三甲基氰硅烷 、 苯甲醛 在 titanium(IV) isopropylate 、 4-bromo-2-((E)-((1S,2S,3R,5S)-3-(hydroxymethyl)-2,6,6-trimethylbicyclo[3.1.1]heptan-2-ylimino)methyl)phenol 、 盐酸 、 水 作用下， 以 二氯甲烷 、 乙酸乙酯 为溶剂， 反应 60.0h， 以99%的产率得到扁桃腈
  参考文献：
  名称：

  α-Pinene-type chiral Schiff bases as tridentate ligands in asymmetric addition reactions

  摘要：

  A group of tridentate Schiff bases derived from (+)-alpha-pinene were synthesized. The steric effects in the transition state, the importance of pi-pi stacking interactions as well as the electronic effects of aryl aldehydes according to Hammett constant values in the enantioselective addition of Et2Zn to aldehydes with the use of Schiff bases as chiral ligands are described. Also, a variety of aldehydes were cyanated using a catalyst prepared in situ from titanium tetraisopropoxide and chiral Schiff bases. The influence of a conjugated double-bond in the cyanation substrates on enantioselectivity was observed. The chemical structures of the chiral Schiff base-titanium alkoxide complexes are discussed based on their H-1 and C-13 NMR spectra. 3D models of the Zn-2-complex catalyst and Ti-complex catalyst containing alpha-pinane-type Schiff bases based on X-ray diffraction experiments are postulated. The models presented were consistent with the reported chirality of the addition product and observed ee. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2011.03.013