(E,2R)-2-[[(2S,4S,5S)-3,4-dimethyl-2-oxo-5-phenyl-1,3,2lambda5-oxazaphospholidin-2-yl]oxy]-2-ethylpent-3-enenitrile | 195433-98-8

• 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: (E,2R)-2-[[(2S,4S,5S)-3,4-dimethyl-2-oxo-5-phenyl-1,3,2lambda5-oxazaphospholidin-2-yl]oxy]-2-ethylpent-3-enenitrile
• 英文别名: (E,2R)-2-[[(2S,4S,5S)-3,4-dimethyl-2-oxo-5-phenyl-1,3,2λ5-oxazaphospholidin-2-yl]oxy]-2-ethylpent-3-enenitrile
• CAS: 195433-98-8
• 化学式: C₁₇H₂₃N₂O₃P
• 分子量: 334.355
• InChiKey: MTYWTTBRUXYAKD-WRASALNSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  23
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 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：

  (E,2R)-2-[[(2S,4S,5S)-3,4-dimethyl-2-oxo-5-phenyl-1,3,2lambda5-oxazaphospholidin-2-yl]oxy]-2-ethylpent-3-enenitrile 在 三异丙氧基氯化钛 、 溶剂黄146 、 4-2-吡啶偶氮-N,N-二甲氧基苯胺 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 正己烷 为溶剂， 反应 4.0h， 生成 (2R)-2-ethyl-2-hydroxypentanenitrile
  参考文献：
  名称：

  A General Strategy to Enantiomerically Pure Aliphatic and Olefinic Ketone Cyanohydrins by Stereoselective Alkylation of Umpoled Aldehyde Derivatives

  摘要：

  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.

  DOI：

  10.1021/jo970854a
• 作为产物：
  描述：

  (E)-2-hydroxypent-3-enenitrile 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 4.33h， 生成 (E,2R)-2-[[(2S,4S,5S)-3,4-dimethyl-2-oxo-5-phenyl-1,3,2lambda5-oxazaphospholidin-2-yl]oxy]-2-ethylpent-3-enenitrile
  参考文献：
  名称：

  A General Strategy to Enantiomerically Pure Aliphatic and Olefinic Ketone Cyanohydrins by Stereoselective Alkylation of Umpoled Aldehyde Derivatives

  摘要：

  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.

  DOI：

  10.1021/jo970854a

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.