(1R,2R,6S,7R,9R)-4,4-Dimethyl-8-[(S)-1-phenylethyl]-3,5-dioxa-8-azatricyclo[5.2.1.0^2,6]decane-9-carboxylic acid methyl ester | 347381-71-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (1R,2R,6S,7R,9R)-4,4-Dimethyl-8-[(S)-1-phenylethyl]-3,5-dioxa-8-azatricyclo[5.2.1.0^2,6]decane-9-carboxylic acid methyl ester
• CAS: 347381-71-9
• 化学式: C₁₉H₂₅NO₄
• 分子量: 331.412
• InChiKey: MXPBHTWIMYEJNB-HJHUUBBFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.51
• 重原子数：
  24.0
• 可旋转键数：
  3.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.63
• 拓扑面积：
  48.0
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  (1R,2R,6S,7R,9R)-4,4-Dimethyl-8-[(S)-1-phenylethyl]-3,5-dioxa-8-azatricyclo[5.2.1.0^2,6]decane-9-carboxylic acid methyl ester 在 lithium aluminium tetrahydride 、 cerium(III) chloride 、 草酰氯 、 TEA 、 二甲基亚砜 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 反应 1.0h， 生成 1-[(1R,2R,6S,7R,9R)-4,4-Dimethyl-8-((S)-1-phenyl-ethyl)-3,5-dioxa-8-aza-tricyclo[5.2.1.0^2,6]dec-9-yl]-ethanol
  参考文献：
  名称：

  Remote Dipole Effects as a Means to Accelerate [Ru(amino alcohol)]-Catalyzed Transfer Hydrogenation of Ketones

  摘要：

  A new generation of 2-azanolbornyl amino alcohol ligands for the catalytic transfer hydrogenation reaction of aromatic ketones was synthesized. Extremely active catalysts were formed by introducing a ketal functionality at the I car end of the ligand, Acetophenone was reduced in 96% cc at low catalyst loading, substrate: to catalyst ratio, S/C 5000, within 90 minutes with isopropyl alcohol as the hydrogen donor. It was round that the dioxolane substituent in the ligand increased the turnover frequency, TOF50 from 1050 h(-1) to 3000 h(-1) at an S/C ratio of 1000, Introduction of a methyl group at the carbinol carbon resulted in TOF50 as high as 8500 h(-1), Transfer hydrogenation of a range of aromatic ketones was evaluated and found to reach completion within 30 minutes at room temperature, and excellent enantioselectivity, up to 99% cc, was obtained. A possible explanation for the enhanced activity was provided by density functional calculations, which showed that the presence of a remote dipole in the ligand lowered the transition state energy.

  DOI：

  10.1002/1521-3765(20010401)7:7<1431::aid-chem1431>3.0.co;2-l
• 作为产物：
  描述：

  methyl (1R,3R,4S)-2-((S)-1-phenylethyl)-2-azabicyclo[2.2.1]hept-5-ene-3-carboxylate 在 四氧化锇 、 N-甲基吲哚酮 、 对甲苯磺酸 作用下， 以 甲醇 、 叔丁醇 为溶剂， 反应 24.0h， 生成 (1R,2R,6S,7R,9R)-4,4-Dimethyl-8-[(S)-1-phenylethyl]-3,5-dioxa-8-azatricyclo[5.2.1.0^2,6]decane-9-carboxylic acid methyl ester
  参考文献：
  名称：

  Remote Dipole Effects as a Means to Accelerate [Ru(amino alcohol)]-Catalyzed Transfer Hydrogenation of Ketones

  摘要：

  A new generation of 2-azanolbornyl amino alcohol ligands for the catalytic transfer hydrogenation reaction of aromatic ketones was synthesized. Extremely active catalysts were formed by introducing a ketal functionality at the I car end of the ligand, Acetophenone was reduced in 96% cc at low catalyst loading, substrate: to catalyst ratio, S/C 5000, within 90 minutes with isopropyl alcohol as the hydrogen donor. It was round that the dioxolane substituent in the ligand increased the turnover frequency, TOF50 from 1050 h(-1) to 3000 h(-1) at an S/C ratio of 1000, Introduction of a methyl group at the carbinol carbon resulted in TOF50 as high as 8500 h(-1), Transfer hydrogenation of a range of aromatic ketones was evaluated and found to reach completion within 30 minutes at room temperature, and excellent enantioselectivity, up to 99% cc, was obtained. A possible explanation for the enhanced activity was provided by density functional calculations, which showed that the presence of a remote dipole in the ligand lowered the transition state energy.

  DOI：

  10.1002/1521-3765(20010401)7:7<1431::aid-chem1431>3.0.co;2-l