(1R*,2S*)-1-(N,N-diisopropylamino)-1-oxo-2-tert-butyl-Δ³-phospholene | 143237-83-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 磷环化合物
• 英文名称: (1R*,2S*)-1-(N,N-diisopropylamino)-1-oxo-2-tert-butyl-Δ³-phospholene
• 英文别名: (1R,2S)-2-tert-butyl-1-oxo-N,N-di(propan-2-yl)-2,5-dihydro-1lambda5-phosphol-1-amine；(1R,2S)-2-tert-butyl-1-oxo-N,N-di(propan-2-yl)-2,5-dihydro-1λ5-phosphol-1-amine
• CAS: 143237-83-6
• 化学式: C₁₄H₂₈NOP
• 分子量: 257.356
• InChiKey: ZCYIJQUBRQZAEH-SUMWQHHRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  二氯-N,N-二异丙基亚磷酰胺 在 三氯化铝 、 乙二胺四乙酸 、 碳酸氢钠 作用下， 反应 10.5h， 生成 (1R*,2S*)-1-(N,N-diisopropylamino)-1-oxo-2-tert-butyl-Δ³-phospholene
  参考文献：
  名称：

  Preparation of (2S*,5S*)-2,5-dibenzylphospholanic acid

  摘要：

  The cheletropic cycloaddition of [CIP(N-i-Pr2)]+AlCl4- with 1-substituted dienes at 0-degrees-C afforded 1-(N,N-diisoprophyamino)-1-chloro-2-alkyl-DELTA-3-phospholenium tetrachloroaluminates. The stereoselectivity of these reactions ranged from 5:1 to 100:0. Hydrolysis of the cycloadducts afforded a diastereomeric mixture of 1-(N,N-diisopropylamino)-1-oxo-2-alkyl-DELTA-3-phospholenes. The ratio of the DELTA-3-phospholene amides differed significantly from the ratio of the intermediate DELTA-3-phospholenium ions, implying that the hydrolysis reactions occurred via five-coordinate phosphoranes which underwent pseudorotation prior to elimination of HCI. Hydrogenation of the DELTA-3-phospholene amides afforded saturated phospholane amides which underwent regioselective deprotonation and subsequent stereospecific alkylation reactions with alkyl halides. 1-(N,N-Diisopropylamino)-1-oxo-2,5-dimethyl- and -2,5-dibenzylphospholanes (10a and 10b) were converted by acid-promoted hydrolysis to (2R*,5R*)-2,5-dimethyl- and (2S*,5S*)-2,5-dibenzylphospholanic acid (12a and 12b), respectively.

  DOI：

  10.1021/jo00045a035

文献信息

• Polniaszek, Richard P., Phosphorus, Sulfur and Silicon and the Related Elements, 1993, vol. 75, # 1-4, p. 127 - 130
  作者：Polniaszek, Richard P.

  DOI：——

  日期：——
• Preparation of (2S*,5S*)-2,5-dibenzylphospholanic acid
  作者：Richard P. Polniaszek

  DOI：10.1021/jo00045a035

  日期：1992.9

  The cheletropic cycloaddition of [CIP(N-i-Pr2)]+AlCl4- with 1-substituted dienes at 0-degrees-C afforded 1-(N,N-diisoprophyamino)-1-chloro-2-alkyl-DELTA-3-phospholenium tetrachloroaluminates. The stereoselectivity of these reactions ranged from 5:1 to 100:0. Hydrolysis of the cycloadducts afforded a diastereomeric mixture of 1-(N,N-diisopropylamino)-1-oxo-2-alkyl-DELTA-3-phospholenes. The ratio of the DELTA-3-phospholene amides differed significantly from the ratio of the intermediate DELTA-3-phospholenium ions, implying that the hydrolysis reactions occurred via five-coordinate phosphoranes which underwent pseudorotation prior to elimination of HCI. Hydrogenation of the DELTA-3-phospholene amides afforded saturated phospholane amides which underwent regioselective deprotonation and subsequent stereospecific alkylation reactions with alkyl halides. 1-(N,N-Diisopropylamino)-1-oxo-2,5-dimethyl- and -2,5-dibenzylphospholanes (10a and 10b) were converted by acid-promoted hydrolysis to (2R*,5R*)-2,5-dimethyl- and (2S*,5S*)-2,5-dibenzylphospholanic acid (12a and 12b), respectively.