tert-Butyl (4S)-3-<(2R)-2-(N-benzylamino)propionyl>-1-methyl-2-oxoimidazolidine-4-carboxylate | 157163-04-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: tert-Butyl (4S)-3-<(2R)-2-(N-benzylamino)propionyl>-1-methyl-2-oxoimidazolidine-4-carboxylate
• 英文别名: tert-butyl (4S)-1-methyl-3-((2R)-benzylaminopropionyl)-2-oxoimidazolidine-4-carboxylate；tert-butyl (4S)-3-[(2R)-2-(benzylamino)propanoyl]-1-methyl-2-oxoimidazolidine-4-carboxylate
• CAS: 157163-04-7
• 化学式: C₁₉H₂₇N₃O₄
• 分子量: 361.441
• InChiKey: UZTMJFIBGOBSSJ-HIFRSBDPSA-N

物化性质

• 沸点：
  458.2±55.0 °C(predicted)
• 密度：
  1.170±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  26
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  79
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  tert-Butyl (4S)-3-<(2R)-2-(N-benzylamino)propionyl>-1-methyl-2-oxoimidazolidine-4-carboxylate 在 正丁基锂 、 potassium tert-butylate 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 反应 1.5h， 生成 tert-butyl (4S)-3-(2-bromo-4-methylpentanoyl)-1-methyl-2-oxoimidazolidine-4-carboxylate
  参考文献：
  名称：

  Stereospecific Amination by Dynamic Kinetic Resolution Utilizing 2-Oxoimidazolidine-4-carboxylate as a Novel Chiral Auxiliary

  摘要：

  A novel type of stereospecific amination by dynamic kinetic resolution using (4S)-2-oxoimidazolidine-4-carboxylate (1) as a chiral auxiliary was developed. A reaction of a diastereomeric mixture of (4S)-3-[(2RS)-2-bromoacyl]-2-oxoimidazolidine-4-carboxylates 4 with an amine in the presence of a base in HMPA predominantly afforded (4S)-3-[(2R)-2-(alkylamino)acyl]-2-oxoimidazolidine-4-carboxylates (S,R)-7 in good yields. The reaction proceeded by stereospecific S(N)2 type amination incorporated with rapid interconversion between the substrates (S,S)-4 and (S,R)-4. Mechanistic study suggested that the unique stereoselectivity was induced through the interaction between an amine and the ester group of (S,S)-4 in the transition state. The chiral auxiliary was easily removed with alkoxide anion to afford the alpha-amino acid synthon in good yields.

  DOI：

  10.1021/jo00126a029
• 作为产物：
  描述：

  tert.-butyl (4S)-1-methyl-3-(2-bromopropionyl)-2-oxo-imidazolidine-4-carboxylate 、 苄胺 在 potassium carbonate 作用下， 以 六甲基磷酰三胺 为溶剂， 反应 14.0h， 生成 tert-Butyl (4S)-3-<(2S)-2-(N-benzylamino)propionyl>-1-methyl-2-oxoimidazolidine-4-carboxylate 、 tert-Butyl (4S)-3-<(2R)-2-(N-benzylamino)propionyl>-1-methyl-2-oxoimidazolidine-4-carboxylate
  参考文献：
  名称：

  Stereospecific Amination by Dynamic Kinetic Resolution Utilizing 2-Oxoimidazolidine-4-carboxylate as a Novel Chiral Auxiliary

  摘要：

  A novel type of stereospecific amination by dynamic kinetic resolution using (4S)-2-oxoimidazolidine-4-carboxylate (1) as a chiral auxiliary was developed. A reaction of a diastereomeric mixture of (4S)-3-[(2RS)-2-bromoacyl]-2-oxoimidazolidine-4-carboxylates 4 with an amine in the presence of a base in HMPA predominantly afforded (4S)-3-[(2R)-2-(alkylamino)acyl]-2-oxoimidazolidine-4-carboxylates (S,R)-7 in good yields. The reaction proceeded by stereospecific S(N)2 type amination incorporated with rapid interconversion between the substrates (S,S)-4 and (S,R)-4. Mechanistic study suggested that the unique stereoselectivity was induced through the interaction between an amine and the ester group of (S,S)-4 in the transition state. The chiral auxiliary was easily removed with alkoxide anion to afford the alpha-amino acid synthon in good yields.

  DOI：

  10.1021/jo00126a029

文献信息

• 2-oxoimidazolidine-4-carboxylate as a novel chiral auxiliary for kinetic resolution
  作者：Hitoshi Kubota、Akira Kubo、Ken-ichi Nunami

  DOI：10.1016/s0040-4039(00)76842-0

  日期：1994.5

  A kinetic resolution by stereospecific amination using 2-oxoimidazolidine-4-carboxylate as a novel chiral auxiliary was investigated. The reaction of tert-butyl (4S)-1-methyl-3-(2-bromopropionyl)-2-oxoimidazolidine-4-carboxylate (5) with an equimolar benzylamine in CH2Cl2 proceeded stereospecifically to afford tert-butyl (4S)-1-methyl-3-((2R)-2-benzylaminopropionyl)-2-oxoimidazolidine-4-carboxylate ((S,R)-4) in a good yield, while (S,R)-5 was recovered quantitatively.