2-(1'-Hydroxy-2'-methylprop-2'-enyl)-2,3,3a,4,5,6,7,7a-octahydro-1,3-dibenzyl-1H-1,3,2-benzodiazaphosphole 2-oxide

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-(1'-Hydroxy-2'-methylprop-2'-enyl)-2,3,3a,4,5,6,7,7a-octahydro-1,3-dibenzyl-1H-1,3,2-benzodiazaphosphole 2-oxide
• 英文别名: 1-[(3aR,7aR)-1,3-dibenzyl-2-oxo-3a,4,5,6,7,7a-hexahydrobenzo[d][1,3,2]diazaphosphol-2-yl]-2-methylprop-2-en-1-ol
• 化学式: C₂₄H₃₁N₂O₂P
• 分子量: 410.496
• InChiKey: NWHWCTKRLDSWHS-YOQGVNIDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  29
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  43.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  2-甲基丙烯醛 、 (3aS,7aS)-1,3-Dibenzyl-octahydro-benzo[1,3,2]diazaphosphole 2-oxide 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 以60%的产率得到2-(1'-Hydroxy-2'-methylprop-2'-enyl)-2,3,3a,4,5,6,7,7a-octahydro-1,3-dibenzyl-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

文献信息

• Reactions of Chiral Phosphorous Acid Diamides: The Asymmetric Synthesis of Chiral .alpha.-Hydroxy Phosphonamides, Phosphonates, and Phosphonic Acids
  作者：Vincent J. Blazis、Kevin J. Koeller、Christopher D. Spilling

  DOI：10.1021/jo00109a025

  日期：1995.2

  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.