1,3,2-Oxazaphospholidine, 2-chloro-3,4-dimethyl-5-phenyl-, 2-oxide | 13897-77-3

• 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: 1,3,2-Oxazaphospholidine, 2-chloro-3,4-dimethyl-5-phenyl-, 2-oxide
• 英文别名: (2R,4S,5R)-2-chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidin-2-one；(2S,4S,5S)-2-Chloro-3,4-dimethyl-5-phenyl-1,3,2-oxazaphospholidin-2-one；(4S)-2-chloro-3,4r-dimethyl-5t-phenyl-[1,3,2]oxazaphospholidine 2ξ-oxide；N,O-(Ξ)-chlorophosphoryl-(+)-pseudoephedrine
• CAS: 13897-77-3；28080-18-4；28080-19-5；31060-10-3；31060-12-5；53625-09-5；53625-11-9；54750-12-8；54750-13-9；72691-41-9；149116-52-9
• 化学式: C₁₀H₁₃ClNO₂P
• 分子量: 245.645
• InChiKey: OXYULDFETWMUMU-AQZZLOACSA-N

物化性质

• 熔点：
  79-80 °C
• 沸点：
  320.2±45.0 °C(Predicted)
• 密度：
  1.30±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.43
• 重原子数：
  15.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  29.54
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  1,3,2-Oxazaphospholidine, 2-chloro-3,4-dimethyl-5-phenyl-, 2-oxide 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
• 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， 生成 1,3,2-Oxazaphospholidine, 2-chloro-3,4-dimethyl-5-phenyl-, 2-oxide
  参考文献：
  名称：

  Schrader, Thomas, Angewandte Chemie, 1995, vol. 107, # 8, p. 1001 - 1002

  摘要：

  DOI：

文献信息

• Rearrangements of Nonracemic Vinyl Phosphates to .beta.-Keto Phosphonates
  作者：Yi-Zhong An、Jian Guo An、David F. Wiemer

  DOI：10.1021/jo00105a042

  日期：1994.12

  A series of chiral auxiliaries has been tested for viability in the vinyl phosphate/beta-keto phosphonate rearrangement. While dienyl phosphates derived from ephedrine, pseudoephedrine, and isopinocampheol succumbed to competing elimination reactions, ones derived from menthol and (S)-2-methylbutanol were found to undergo rearrangement to the desired beta-keto phosphonates. The bis((S)2-methylbultyl) phosphorochloridate then was used to prepare the vinyl phosphates of the prochiral ketone 4-methylcyclohexanone, and modest diastereoselectivity was observed upon rearrangement of these phosphates to the corresponding beta-keto phosphonates. The de of this rearrangement was established by degradation of the beta-keto phosphonate to 3-methyladipic acid and determination of the optical rotation. This sequence allowed identification of the major rearrangement product as the 4R-diastereomer of beta-keto phosphonate 13. Finally, two other prochiral cyclohexanones were found to be suitable substrates for the vinyl phosphate/beta-keto phosphonate rearrangement.