tert-butyl 2-[N-(p-methoxyphenyl)imino]-3-chloro-3,3-difluoropropanoate | 278611-76-0

• 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: tert-butyl 2-[N-(p-methoxyphenyl)imino]-3-chloro-3,3-difluoropropanoate
• 英文别名: Tert-butyl 3-chloro-3,3-difluoro-2-(4-methoxyphenyl)iminopropanoate
• CAS: 278611-76-0
• 化学式: C₁₄H₁₆ClF₂NO₃
• 分子量: 319.736
• InChiKey: NLTGVKXNSGOXSI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  21
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  47.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  tert-butyl 2-[N-(p-methoxyphenyl)imino]-3-chloro-3,3-difluoropropanoate 在 palladium(II) trifluoroacetate 氢气 、 (R)-2,2'-bis(diphenylphosphanyl)-1,1'-binaphthyl 作用下， 以 2,2,2-三氟乙醇 、 丙酮 为溶剂， 20.0 ℃ 、10.13 MPa 条件下， 反应 24.0h， 生成 t-butyl 3-chloro-3,3-difluoro-(R)-2-(4-methoxyphenylamino)propanoate 、 (S)-3-Chloro-3,3-difluoro-2-(4-methoxy-phenylamino)-propionic acid tert-butyl ester
  参考文献：
  名称：

  Pd催化氟代醇中的α-氟化亚氨基酯的不对称加氢：氟代α-氨基酸衍生物的新型催化对映选择性合成。

  摘要：

  [图：见正文]在氢气压力下，催化量的三氟乙酸钯（II）和2,2'-双（二苯基膦基）-1,1'-联萘基（BINAP）促进了α-氟化亚氨基酯的不对称氢化，从而提供了高纯度的对映体富集的β-氟代α-氨基酯。通过使用氟化醇（例如2,2,2-三氟乙醇）（最高ee为91％），可以大大提高收率和ee。

  DOI：

  10.1021/ol0002471
• 作为产物：
  描述：

  2-chloro-2,2-difluoro-N-(4-methoxyphenyl)ethanimidoyl chloride 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 地昔帕明 、 potassium carbonate 、 sodium iodide 作用下， 以 丙酮 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 反应 120.0h， 生成 tert-butyl 2-[N-(p-methoxyphenyl)imino]-3-chloro-3,3-difluoropropanoate
  参考文献：
  名称：

  Palladium-Catalyzed tert-Butoxycarbonylation of Trifluoroacetimidoyl Iodides

  摘要：

  A modification and details of the palladium-catalyzed tert-butoxycarbonylation of 2,2,2-trifluoroacetimidoyl iodides 1, which gave the iminocarboxylates 2, one of the promising precursors to fluorinated ol-amino acids, are described. The Pd-catalyzed carbonylation reaction was remarkably promoted by the use of DMF or DMI as an additive, enough to achieve the selective formation of tert-butyl iminoesters. Nucleophilic alkylation of the imine moiety of 2 and subsequent removal of N- and O-protecting groups gave a variety of 2-substituted 2-amino-3,3,3-trifluoropropanoic acid derivatives 3 in high yields.

  DOI：

  10.1021/jo991917n

文献信息

• Palladium-Catalyzed <i>tert</i>-Butoxycarbonylation of Trifluoroacetimidoyl Iodides
  作者：Hideki Amii、Yosuke Kishikawa、Katsuhiko Kageyama、Kenji Uneyama

  DOI：10.1021/jo991917n

  日期：2000.6.1

  A modification and details of the palladium-catalyzed tert-butoxycarbonylation of 2,2,2-trifluoroacetimidoyl iodides 1, which gave the iminocarboxylates 2, one of the promising precursors to fluorinated ol-amino acids, are described. The Pd-catalyzed carbonylation reaction was remarkably promoted by the use of DMF or DMI as an additive, enough to achieve the selective formation of tert-butyl iminoesters. Nucleophilic alkylation of the imine moiety of 2 and subsequent removal of N- and O-protecting groups gave a variety of 2-substituted 2-amino-3,3,3-trifluoropropanoic acid derivatives 3 in high yields.
• Pd-Catalyzed Asymmetric Hydrogenation of α-Fluorinated Iminoesters in Fluorinated Alcohol:  A New and Catalytic Enantioselective Synthesis of Fluoro α-Amino Acid Derivatives
  作者：Hajime Abe、Hideki Amii、Kenji Uneyama

  DOI：10.1021/ol0002471

  日期：2001.2.1

  [figure: see text] Under hydrogen pressure, a catalytic amount of palladium(II) trifluoroacetate and 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP) promoted asymmetric hydrogenation of alpha-fluorinated iminoesters to afford highly enantioenriched beta-fluorinated alpha-amino esters. The yield and ee were much improved by employing fluorinated alcohols such as 2,2,2-trifluoroethanol (up to 91%

  [图：见正文]在氢气压力下，催化量的三氟乙酸钯（II）和2,2'-双（二苯基膦基）-1,1'-联萘基（BINAP）促进了α-氟化亚氨基酯的不对称氢化，从而提供了高纯度的对映体富集的β-氟代α-氨基酯。通过使用氟化醇（例如2,2,2-三氟乙醇）（最高ee为91％），可以大大提高收率和ee。