2-(1'-Hydroxy-3'-phenyl-(E)-prop-2'-enyl)-2,3,3a,4,5,6,7,7a-octahydro-1,3-bis(2,2-dimethylpropyl)-1H-1,3,2-benzodiazaphosphole 2-oxide | 162680-99-1

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂醇
• 英文名称: 2-(1'-Hydroxy-3'-phenyl-(E)-prop-2'-enyl)-2,3,3a,4,5,6,7,7a-octahydro-1,3-bis(2,2-dimethylpropyl)-1H-1,3,2-benzodiazaphosphole 2-oxide
• 英文别名: (E,1S)-1-[(3aR,7aR)-1,3-bis(2,2-dimethylpropyl)-2-oxo-3a,4,5,6,7,7a-hexahydrobenzo[d][1,3,2]diazaphosphol-2-yl]-3-phenylprop-2-en-1-ol
• CAS: 162680-99-1
• 化学式: C₂₅H₄₁N₂O₂P
• 分子量: 432.587
• InChiKey: NDTHCMGNBOFWJN-VQMSTHNPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  30
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  43.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-(1'-Hydroxy-3'-phenyl-(E)-prop-2'-enyl)-2,3,3a,4,5,6,7,7a-octahydro-1,3-bis(2,2-dimethylpropyl)-1H-1,3,2-benzodiazaphosphole 2-oxide 在 盐酸 作用下， 以 1,4-二氧六环 为溶剂， 反应 24.0h， 生成 (S)-(-)-<1-Hydroxy-3-phenyl-2(E)-propenyl>phosphonic acid
  参考文献：
  名称：

  Reactions of Chiral Phosphorous Acid Diamides: The Asymmetric Synthesis of Chiral .alpha.-Hydroxy Phosphonamides, Phosphonates, and Phosphonic Acids

  摘要：

  Addition of aldehydes to the anions of chiral phosphorous acid diamides in THF solution gave a-hydroxy phosphonamides in good yield. The diastereoselectivity was strongly dependent upon the diamide used and ranged from poor to good. The phosphorous acid diamides 2a and 2b (R(1) = -(CH2)4-,R(2) = CH(2)Ph and CH(2)CMe(3), respectively) gave the best selectivity, and their reactions with a range of aldehydes were studied. Diamide 2b consistently gave good selectivities, whereas diamide 2a was only moderately selective. Aromatic, aliphatic, and unsaturated aldehydes are tolerated under the reaction conditions. The phosphonamides were hydrolyzed with aqueous HCl in dioxane to give a-hydroxy phosphonic acids. While direct methanolysis of the phosphonamides was unsuccessful, methylation of the phosphonic acids with diazomethane gave alpha-hydroxy dimethylphosphonates.

  DOI：

  10.1021/jo00109a025
• 作为产物：
  描述：

  反式肉桂醛 、 (3aR,7aR)-2,3,3a,4,5,6,7,7a-Octahydro-1,3-bis(2,2-dimethylpropyl)-1H-1,2,3-benzodiazaphosphole-2-oxide 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 生成 2-(1'-Hydroxy-3'-phenyl-(E)-prop-2'-enyl)-2,3,3a,4,5,6,7,7a-octahydro-1,3-bis(2,2-dimethylpropyl)-1H-1,3,2-benzodiazaphosphole 2-oxide 、 2-(1'-Hydroxy-3'-phenyl-(E)-prop-2'-enyl)-2,3,3a,4,5,6,7,7a-octahydro-1,3-bis(2,2-dimethylpropyl)-1H-1,3,2-benzodiazaphosphole 2-oxide
  参考文献：
  名称：

  Reactions of Chiral Phosphorous Acid Diamides: The Asymmetric Synthesis of Chiral .alpha.-Hydroxy Phosphonamides, Phosphonates, and Phosphonic Acids

  摘要：

  Addition of aldehydes to the anions of chiral phosphorous acid diamides in THF solution gave a-hydroxy phosphonamides in good yield. The diastereoselectivity was strongly dependent upon the diamide used and ranged from poor to good. The phosphorous acid diamides 2a and 2b (R(1) = -(CH2)4-,R(2) = CH(2)Ph and CH(2)CMe(3), respectively) gave the best selectivity, and their reactions with a range of aldehydes were studied. Diamide 2b consistently gave good selectivities, whereas diamide 2a was only moderately selective. Aromatic, aliphatic, and unsaturated aldehydes are tolerated under the reaction conditions. The phosphonamides were hydrolyzed with aqueous HCl in dioxane to give a-hydroxy phosphonic acids. While direct methanolysis of the phosphonamides was unsuccessful, methylation of the phosphonic acids with diazomethane gave alpha-hydroxy dimethylphosphonates.

  DOI：

  10.1021/jo00109a025