(Z)-3-Benzylamino-4,4,4-trifluoro-2-methyl-but-2-enoic acid ethyl ester | 203061-92-1

• 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: (Z)-3-Benzylamino-4,4,4-trifluoro-2-methyl-but-2-enoic acid ethyl ester
• 英文别名: ethyl (Z)-3-(benzylamino)-4,4,4-trifluoro-2-methylbut-2-enoate
• CAS: 203061-92-1
• 化学式: C₁₄H₁₆F₃NO₂
• 分子量: 287.282
• InChiKey: KDLDONJYMXKQOX-BENRWUELSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  38.3
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (Z)-3-Benzylamino-4,4,4-trifluoro-2-methyl-but-2-enoic acid ethyl ester 在 三乙胺 作用下， 以 甲苯 为溶剂， 生成 3-[(E)-Benzylimino]-4,4,4-trifluoro-2-methyl-butyric acid ethyl ester
  参考文献：
  名称：

  Biomimetic Transamination of α-Alkyl β-Keto Carboxylic Esters. Chemoenzymatic Approach to the Stereochemically Defined α-Alkyl β-Fluoroalkyl β-Amino Acids

  摘要：

  Biomimetic transamination of the commercially available ethyl 2-methyl-3-keto-4,4,4-trifluorobutyrate (4) with benzylamine was shown to provide a simple access to the 2-methyl-3-amino-4,4,4-trifluorobutanoic acids, a hitherto unknown biologically relevant beta-amino acid. In sharp contrast to the alpha-unsubstituted beta-keto carboxylic esters the transamination of alpha-methyl beta-keto carboxylic ester 4 proceeds under mild reaction conditions, presumably, due to relative instability of the intermediate (Z)-enamine 6. Diastereoselectivity of the process was found to be controlled by the nature of the base-catalyst allowing for a stereodivergent preparation of (2R*,3S*)-8a and (2R*,3R*)-8b diastereomers as dominant reaction products. Preparation of all four diastereo- and enantiomerically pure optical isomers of the 2-methyl-3-amino-4,4,4-trifluorobutanoic acid was effectively accomplished by penicillin acylase-catalyzed resolution of the corresponding diastereomerically pure N-phenylacetyl derivatives. The whole process, a stereocontrolled chemoenzymatic approach, including the diastereoselective base-catalyzed [1,3]-proton shift reaction and the enantioselective penicillin acylase-catalyzed resolution, employs a simple set of reactions, inexpensive reagents, and mild reaction conditions, that would render it methodologically useful for preparing biologically interesting alpha,beta-disubstituted fluorinated beta-amino acids.

  DOI：

  10.1021/jo971777m
• 作为产物：
  描述：

  2-甲基-4,4,4-三氟乙酰乙酸乙酯 、 苄胺 以15%的产率得到(Z)-3-Benzylamino-4,4,4-trifluoro-2-methyl-but-2-enoic acid ethyl ester
  参考文献：
  名称：

  Biomimetic Transamination of α-Alkyl β-Keto Carboxylic Esters. Chemoenzymatic Approach to the Stereochemically Defined α-Alkyl β-Fluoroalkyl β-Amino Acids

  摘要：

  Biomimetic transamination of the commercially available ethyl 2-methyl-3-keto-4,4,4-trifluorobutyrate (4) with benzylamine was shown to provide a simple access to the 2-methyl-3-amino-4,4,4-trifluorobutanoic acids, a hitherto unknown biologically relevant beta-amino acid. In sharp contrast to the alpha-unsubstituted beta-keto carboxylic esters the transamination of alpha-methyl beta-keto carboxylic ester 4 proceeds under mild reaction conditions, presumably, due to relative instability of the intermediate (Z)-enamine 6. Diastereoselectivity of the process was found to be controlled by the nature of the base-catalyst allowing for a stereodivergent preparation of (2R*,3S*)-8a and (2R*,3R*)-8b diastereomers as dominant reaction products. Preparation of all four diastereo- and enantiomerically pure optical isomers of the 2-methyl-3-amino-4,4,4-trifluorobutanoic acid was effectively accomplished by penicillin acylase-catalyzed resolution of the corresponding diastereomerically pure N-phenylacetyl derivatives. The whole process, a stereocontrolled chemoenzymatic approach, including the diastereoselective base-catalyzed [1,3]-proton shift reaction and the enantioselective penicillin acylase-catalyzed resolution, employs a simple set of reactions, inexpensive reagents, and mild reaction conditions, that would render it methodologically useful for preparing biologically interesting alpha,beta-disubstituted fluorinated beta-amino acids.

  DOI：

  10.1021/jo971777m

文献信息

• Biomimetic Transamination of α-Alkyl β-Keto Carboxylic Esters. Chemoenzymatic Approach to the Stereochemically Defined α-Alkyl β-Fluoroalkyl β-Amino Acids
  作者：Vadim A. Soloshonok、Irina V. Soloshonok、Valery P. Kukhar、Vytas K. Svedas

  DOI：10.1021/jo971777m

  日期：1998.3.1

  Biomimetic transamination of the commercially available ethyl 2-methyl-3-keto-4,4,4-trifluorobutyrate (4) with benzylamine was shown to provide a simple access to the 2-methyl-3-amino-4,4,4-trifluorobutanoic acids, a hitherto unknown biologically relevant beta-amino acid. In sharp contrast to the alpha-unsubstituted beta-keto carboxylic esters the transamination of alpha-methyl beta-keto carboxylic ester 4 proceeds under mild reaction conditions, presumably, due to relative instability of the intermediate (Z)-enamine 6. Diastereoselectivity of the process was found to be controlled by the nature of the base-catalyst allowing for a stereodivergent preparation of (2R*,3S*)-8a and (2R*,3R*)-8b diastereomers as dominant reaction products. Preparation of all four diastereo- and enantiomerically pure optical isomers of the 2-methyl-3-amino-4,4,4-trifluorobutanoic acid was effectively accomplished by penicillin acylase-catalyzed resolution of the corresponding diastereomerically pure N-phenylacetyl derivatives. The whole process, a stereocontrolled chemoenzymatic approach, including the diastereoselective base-catalyzed [1,3]-proton shift reaction and the enantioselective penicillin acylase-catalyzed resolution, employs a simple set of reactions, inexpensive reagents, and mild reaction conditions, that would render it methodologically useful for preparing biologically interesting alpha,beta-disubstituted fluorinated beta-amino acids.