Methyl 3-(Benzylamino)-4,4,4-trifluoro-but-2-enoate | 150618-26-1

• 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: Methyl 3-(Benzylamino)-4,4,4-trifluoro-but-2-enoate
• 英文别名: methyl (Z)-3-(benzylamino)-4,4,4-trifluorobut-2-enoate
• CAS: 150618-26-1
• 化学式: C₁₂H₁₂F₃NO₂
• 分子量: 259.228
• InChiKey: GNZITHNIPVKGNV-YFHOEESVSA-N

物化性质

• 沸点：
  341.3±42.0 °C(Predicted)
• 密度：
  1.232±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 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：

  Methyl 3-(Benzylamino)-4,4,4-trifluoro-but-2-enoate 在 三乙胺 盐酸 作用下， 以 乙醚 为溶剂， 反应 14.0h， 生成 3-氨基-4,4,4-三氟丁酸甲酯
  参考文献：
  名称：

  Transamination of fluorinated β-keto carboxylic esters. A biomimetic approach to β-polyfluoroalkyl-β-amino acids.

  摘要：

  The base-catalyzed isomerization of N-benzylimines (or enamines) of beta-polyfluoroalkyl-beta-ketocarboxylic esters cleanly affords the N-benzylidene derivatives of beta-polyfluoro-beta-aminocarboxylic esters which are hydrolyzed to corresponding amino acids in high overall yields.

  DOI：

  10.1016/s0040-4039(00)73652-5
• 作为产物：
  描述：

  三氟乙酰乙酸甲酯 、 苄胺 在 Dowex-50 (H⁺-form) 作用下， 以 苯 为溶剂， 生成 Methyl 3-(Benzylamino)-4,4,4-trifluoro-but-2-enoate
  参考文献：
  名称：

  Transamination of fluorinated β-keto carboxylic esters. A biomimetic approach to β-polyfluoroalkyl-β-amino acids.

  摘要：

  The base-catalyzed isomerization of N-benzylimines (or enamines) of beta-polyfluoroalkyl-beta-ketocarboxylic esters cleanly affords the N-benzylidene derivatives of beta-polyfluoro-beta-aminocarboxylic esters which are hydrolyzed to corresponding amino acids in high overall yields.

  DOI：

  10.1016/s0040-4039(00)73652-5

文献信息

• Biomimetic base-catalyzed [1,3]-proton shift reaction. A practical synthesis of β-fluoroalkyl-β-amino acids
  作者：Vadim A. Soloshonok、Valery P. Kukhar

  DOI：10.1016/0040-4020(96)00300-6

  日期：1996.5

  An efficient approach to practical synthesis of β-fluoroalkyl-β-amino acids is described. The method consists in the reducing reagent-free base-catalyzed biomimetic transamination reaction between fluorinated β-keto carboxylic esters and benzylamine. This transformation involves two sequential base-catalyzed [1,3]-proton transfers giving rise to corresponding N-benzylidene derivatives as the products

  描述了一种有效合成β-氟烷基-β-氨基酸的有效方法。该方法在于氟化β-酮羧酸酯和苄胺之间的无还原剂的无碱催化的仿生转氨反应。该转变涉及两个连续的碱催化的[1,3]-质子转移，产生相应的N-亚苄基衍生物，作为最终热力学平衡的产物，由氟代烷基的吸电子特性指导。证明了通过应用单手性碱作为这些异构化的催化剂来催化对映体控制的靶向β-氨基酸合成的机会。
• 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.
• Transamination of fluorinated β-keto carboxylic esters. A biomimetic approach to β-polyfluoroalkyl-β-amino acids.
  作者：Vadim A. Soloshonok、Alexander G. Kirilenko、Valery P. Kukhar'、Giuseppe Resnati

  DOI：10.1016/s0040-4039(00)73652-5

  日期：1993.5

  The base-catalyzed isomerization of N-benzylimines (or enamines) of beta-polyfluoroalkyl-beta-ketocarboxylic esters cleanly affords the N-benzylidene derivatives of beta-polyfluoro-beta-aminocarboxylic esters which are hydrolyzed to corresponding amino acids in high overall yields.