2-(1'-Acetoxy-3'-methyl-butyl)-2,3,3a,4,5,6,7,7a-octahydro-1,3-bis(2,2-dimethylpropyl)-1H-1,3,2-benzodiazaphosphole 2-oxide | 156300-73-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物
• 英文名称: 2-(1'-Acetoxy-3'-methyl-butyl)-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: [(1R)-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-methylbutyl] acetate
• CAS: 156300-73-1
• 化学式: C₂₃H₄₅N₂O₃P
• 分子量: 428.596
• InChiKey: VULKYWQCSNPKOZ-NJDAHSKKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  29
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.96
• 拓扑面积：
  49.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2-(1'-Acetoxy-3'-methyl-butyl)-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 、 氢氧化钾 作用下， 生成 (R)-(-)-(1-Hydroxy-3-methylbutyl)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：

  乙酸酐 、 2-(1'-Hydroxy-3'-methyl-butyl)-2,3,3a,4,5,6,7,7a-octahydro-1,3-bis(2,2-dimethylpropyl)-1H-1,3,2-benzodiazaphosphole 2-oxide 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 生成 2-(1'-Acetoxy-3'-methyl-butyl)-2,3,3a,4,5,6,7,7a-octahydro-1,3-bis(2,2-dimethylpropyl)-1H-1,3,2-benzodiazaphosphole 2-oxide 、 2-(1'-Acetoxy-3'-methyl-butyl)-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

文献信息

• Asymmetric synthesis of α-hydroxy- phosphonamides, phosphonates and phosphonic acids
  作者：Vincent J. Blazis、Kevin J. Koeller、Christopher D. Spilling

  DOI：10.1016/0957-4166(94)80002-2

  日期：1994.4

  The addition of the anion of the bicyclic chiral phosphorous acid diamide 1a to aldehydes in THF solution gave alpha-hydroxy phosphonamides in good yield and good diastereoselectivity (54-93% de). The phosphonamides were hydrolyzed with aqueous HCl in dioxane to give alpha-hydroxy phosphonic acids. Methylation of the resulting phosphonic acids with diazomethane gave alpha-hydroxy dimethyl phosphonates without loss of stereochemical integrety.
• A Chiral Bicyclic 1-Acetoxy Phosphonamide
  作者：V. J. Blazis、K. J. Koeller、N. P. Rath、C. D. Spilling

  DOI：10.1107/s0108270194007948

  日期：1995.1.15

  The crystal structure of a chiral non-racemic 1-acetoxy phosphonamide, 2-(1-acetoxy-3-methylbutyl)-1,3-(2,2-dimethylpropyl)-2,3,3a,4,5,6,7,7a-octahydro-1H-1,3,2-benzodiazaphosphole 2-oxide, m.p. = 385.5-386 K, C23H45N2O3P, has been determined by X-ray diffraction. The title compound consists of a five-membered ring with a tetrahedrally coordinated P atom. In addition to the two N atoms of the five-membered ring, the P atom is bonded to an O atom and the C-1 atom of the acetoxylalkyl chain. The five-membered ring is trans fused to a cyclohexane ring in a chair conformation.