trans-1-acetoxy-2-<(diisopropoxyphosphinyl)methyl>cyclohexane

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: trans-1-acetoxy-2-<(diisopropoxyphosphinyl)methyl>cyclohexane
• 英文别名: [(1R,2R)-2-[di(propan-2-yloxy)phosphorylmethyl]cyclohexyl] acetate
• 化学式: C₁₅H₂₉O₅P
• 分子量: 320.366
• InChiKey: MJUGHBGVPXZHQZ-LSDHHAIUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  21
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  甲基磷酸二异丙酯 在 吡啶 、 正丁基锂 、 三氟化硼乙醚 作用下， 反应 12.5h， 生成 trans-1-acetoxy-2-<(diisopropoxyphosphinyl)methyl>cyclohexane
  参考文献：
  名称：

  Phosphonomethylation of cyclohexene oxides

  摘要：

  The tradeoff between synthetic directness and regioselectivity during oxirane ring opening is examined for two strategies used to phosphonomethylate cyclohexene oxide and substituted cyclohexene oxides derived from quinic acid and myo-inositol. Direct phosphonomethylation of the cyclohexene oxides utilizes diisopropyl lithiomethanephosphonate ((C3H7O)2P(O)CH2Li) in combination with boron trifluoride. Another more indirect route to phosphonomethylation begins with reaction of the cyclohexene oxides with (lithiomethyl)dimesitylborane (Mes2BCH2Li). In both reactions, boron plays a key role as either a Lewis acid during opening of the oxirane (diisopropyl lithiomethane-phosphonate/boron trifluoride) or as a stabilizer of an adjacent carbanion in the attacking nucleophile [(lithiomethyl)dimesitylborane]. Regioselectivities for oxirane ring opening using diisopropyl lithiomethanephosphonate/boron trifluoride can be quite modest. By contrast, oxirane ring openings employing (lithiomethyl)dimesitylborane are uniform in the high degree of regioselectivity which is achieved. Factors which might influence the observed regioselectivities during nucleophilic attack on the cyclohexene oxides are also discussed.

  DOI：

  10.1021/jo00079a010

文献信息

• Phosphonomethylation of cyclohexene oxides
  作者：Jean Luc Montchamp、Marie E. Migaud、John W. Frost

  DOI：10.1021/jo00079a010

  日期：1993.12

  The tradeoff between synthetic directness and regioselectivity during oxirane ring opening is examined for two strategies used to phosphonomethylate cyclohexene oxide and substituted cyclohexene oxides derived from quinic acid and myo-inositol. Direct phosphonomethylation of the cyclohexene oxides utilizes diisopropyl lithiomethanephosphonate ((C3H7O)2P(O)CH2Li) in combination with boron trifluoride. Another more indirect route to phosphonomethylation begins with reaction of the cyclohexene oxides with (lithiomethyl)dimesitylborane (Mes2BCH2Li). In both reactions, boron plays a key role as either a Lewis acid during opening of the oxirane (diisopropyl lithiomethane-phosphonate/boron trifluoride) or as a stabilizer of an adjacent carbanion in the attacking nucleophile [(lithiomethyl)dimesitylborane]. Regioselectivities for oxirane ring opening using diisopropyl lithiomethanephosphonate/boron trifluoride can be quite modest. By contrast, oxirane ring openings employing (lithiomethyl)dimesitylborane are uniform in the high degree of regioselectivity which is achieved. Factors which might influence the observed regioselectivities during nucleophilic attack on the cyclohexene oxides are also discussed.