(1'R/S,2S,4S,5S)-2-[(1'-Cyano-1'-phenyl)methoxy]-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidin-2-one | 198906-22-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磷酸及其衍生物
• 英文名称: (1'R/S,2S,4S,5S)-2-[(1'-Cyano-1'-phenyl)methoxy]-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidin-2-one
• 英文别名: 2-[[(2S,4S,5S)-3,4-dimethyl-2-oxo-5-phenyl-1,3,2lambda5-oxazaphospholidin-2-yl]oxy]-2-phenylacetonitrile；2-[[(2S,4S,5S)-3,4-dimethyl-2-oxo-5-phenyl-1,3,2λ5-oxazaphospholidin-2-yl]oxy]-2-phenylacetonitrile
• CAS: 198906-22-8
• 化学式: C₁₈H₁₉N₂O₃P
• 分子量: 342.334
• InChiKey: GYRYPIPDIMXQEW-ZAEURVSHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  62.6
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (1'R/S,2S,4S,5S)-2-[(1'-Cyano-1'-phenyl)methoxy]-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidin-2-one 在 三异丙氧基氯化钛 、 盐酸 、 N,N-二甲基丙烯基脲 、 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 4.17h， 生成 3,3-二乙氧基丙酰肼
  参考文献：
  名称：

  Stereoselective Umpolung Reactions with MetalatedP-Chiral Cyanohydrin Phosphates—Enantioselective Synthesis of Tertiary Cyanohydrins

  摘要：

  AbstractWe present the first cyanohydrin derivative4that allows diastereoselective umpolung reactions. In4the OH group of the cyanohydrin is linked with a chiral phosphate, which can be removed hydrolytically after asymmetric synthesis. Cyclization of pseudoephedrine1dwith POCl3gave2d. This was followed by addition of racemic benzaldehyde cyanohydrin3to give the key intermediate4dwith complete retention of the configuration at phosphorus. Deprotonation of4d, followed by addition of a wide variety of electrophiles afforded the crystalline products5with high diastereomeric excesses (deup to 94%). High asymmetric induction was also achieved for the reaction of4−Li+with acyl halides, α‐bromoacetates, 2‐cycloalkenones, α,β‐unsaturated esters, and γ‐bromoacetates. Lewis acid assisted hydrolysis proceeded without racemization and gave high yields of ketone cyanohydrins6. From the ring‐opened chiral auxiliary7, optically pure pseudoephedrine1was readily recovered by acid hydrolysis. Optically pure (R) and (S) ketone cyanohydrins are now accessible in a very general strategy, which circumvents the substrate limitations of enzymatic synthesis.

  DOI：

  10.1002/chem.19970030815
• 作为产物：
  描述：

  (1S,2S)-2-甲氨基-1-苯基丙-1-醇 在 三乙胺 、 三氯氧磷 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 (1'R/S,2S,4S,5S)-2-[(1'-Cyano-1'-phenyl)methoxy]-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidin-2-one
  参考文献：
  名称：

  Stereoselective Umpolung Reactions with MetalatedP-Chiral Cyanohydrin Phosphates—Enantioselective Synthesis of Tertiary Cyanohydrins

  摘要：

  AbstractWe present the first cyanohydrin derivative4that allows diastereoselective umpolung reactions. In4the OH group of the cyanohydrin is linked with a chiral phosphate, which can be removed hydrolytically after asymmetric synthesis. Cyclization of pseudoephedrine1dwith POCl3gave2d. This was followed by addition of racemic benzaldehyde cyanohydrin3to give the key intermediate4dwith complete retention of the configuration at phosphorus. Deprotonation of4d, followed by addition of a wide variety of electrophiles afforded the crystalline products5with high diastereomeric excesses (deup to 94%). High asymmetric induction was also achieved for the reaction of4−Li+with acyl halides, α‐bromoacetates, 2‐cycloalkenones, α,β‐unsaturated esters, and γ‐bromoacetates. Lewis acid assisted hydrolysis proceeded without racemization and gave high yields of ketone cyanohydrins6. From the ring‐opened chiral auxiliary7, optically pure pseudoephedrine1was readily recovered by acid hydrolysis. Optically pure (R) and (S) ketone cyanohydrins are now accessible in a very general strategy, which circumvents the substrate limitations of enzymatic synthesis.

  DOI：

  10.1002/chem.19970030815