(R)-dimethyl (1-hydroxy-oct-2-ynyl) phosphonate

• 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: (R)-dimethyl (1-hydroxy-oct-2-ynyl) phosphonate
• 英文别名: (1R)-1-dimethoxyphosphoryloct-2-yn-1-ol
• 化学式: C₁₀H₁₉O₄P
• 分子量: 234.232
• InChiKey: GUVGKCXKQXGKAS-SNVBAGLBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  亚磷酸氢二甲酯 、 2-辛醛 、 乙酰氯 在 titanium(IV) isopropylate 、 4(1S,2S)-trans-1,2-cyclohexanediol 、 poly(4-vinyl)pyridine 、 lipase AY 作用下， 以 乙醚 、 乙腈 、 phosphate buffer 为溶剂， 生成 (S)-dimethyl (1-hydroxy-oct-2-ynyl) phosphonate 、 (R)-dimethyl (1-hydroxy-oct-2-ynyl) phosphonate
  参考文献：
  名称：

  The synthesis of 1-hydroxy phosphonates of high enantiomeric excess using sequential asymmetric reactions: titanium alkoxide-catalyzed PC bond formation and kinetic resolution

  摘要：

  Titanium alkoxide-catalyzed asymmetric phosphonylation of aldehydes yields hydroxy phosphonates in moderate to good enantiomeric excess (e.e.s similar to 70%). The hydroxy phosphonates were acetylated and the acetates were subjected to enzyme-catalyzed kinetic resolution. The non-racemic acetates 2 (predominantly (R)-enantiomer) were hydrolyzed with an (R)-enantiomer-selective lipase, resulting predominantly in the hydrolysis of the (R)-isomer (at 85% conversion) to give the alcohols 3 with high e.e. Alternatively, hydrolysis of the minor enantiomeric (S)-acetate to approximately 20% conversion left the enriched (R)-configured acetate with improved e.e. (> 90%). The moderate enantio selectivities obtained in the catalytic P-C bond formation are enhanced during the enzymatic hydrolysis. Furthermore, availability of the non-racemic phosphonates permits the use of less selective enzymes, resulting in higher yields in comparison with the standard resolution of racemic materials. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(01)00303-2