(2S,4S,5S)-2-Chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidin-2-one | 31060-12-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2S,4S,5S)-2-Chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidin-2-one
• 英文别名: (2S,4S,5S)-2-chloro-3,4-dimethyl-5-phenyl-1,3,2lambda5-oxazaphospholidine 2-oxide；(2S,4S,5S)-2-chloro-3,4-dimethyl-5-phenyl-1,3,2λ5-oxazaphospholidine 2-oxide
• CAS: 31060-12-5
• 化学式: C₁₀H₁₃ClNO₂P
• 分子量: 245.645
• InChiKey: OXYULDFETWMUMU-SVIKCVJRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2S,4S,5S)-2-Chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidin-2-one 在 N,N-二甲基丙烯基脲 、 正丁基锂 、 三乙胺 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 0.67h， 生成 (1'R,2S,4S,5S,4''R,6''S)-2-{[1'-Cyano-(7'',7''-dimethylbicyclo[3.1.1]hept-1''-enyl)-1'-phenyl]ethoxy}-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
• 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 (2S,4S,5S)-2-Chloro-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

文献信息

• A General Strategy to Enantiomerically Pure Aliphatic and Olefinic Ketone Cyanohydrins by Stereoselective Alkylation of Umpoled Aldehyde Derivatives
  作者：Christian N. Kirsten、Michael Herm、Thomas H. Schrader

  DOI：10.1021/jo970854a

  日期：1997.10.1

  We present the first general synthesis of optically pure (R)- and (S)-ketone cyanohydrins with olefinic and aliphatic substituents. Consecutive condensations of POCl3 with pseudoephedrine (1) and racemic crotonaldehyde cyanohydrin (3, R = 1-propenyl) lead to the respective cyanohydrin phosphate 4c. Deprotonation, followed by highly stereoselective alkylation and a single chromatographic purification step, afford diastereomerically pure ketone cyanohydrin phosphates 5a-e. From these, enantiomerically pure tertiary cyanohydrins 6a-e can be obtained by mild Lewis acid-assisted hydrolysis. Pseudoephedrine is simultaneously recovered without loss of optical purity. The unsaturated alkylation products 5a-d are readily hydrogenated with diimide to aliphatic cyanohydrin phosphates 5f-i, which can be cleaved to furnish the free optically pure cyanohydrins 6f-i. Thus a broad variety of both saturated and unsaturated ketone cyanohydrins with R > Et becomes accessible in optically pure form for the first time. The free cyanohydrins are easily converted to optically pure alpha-branched alpha-hydroxy acids.
• Stereoselective Umpolung Reactions with MetalatedP-Chiral Cyanohydrin Phosphates—Enantioselective Synthesis of Tertiary Cyanohydrins
  作者：Thomas Schrader

  DOI：10.1002/chem.19970030815

  日期：1997.8

  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.