L-7-(trifluoromethyl)tryptophan | 143266-28-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: L-7-(trifluoromethyl)tryptophan
• 英文别名: (S)-1-carboxy-2-(7-(trifluoromethyl)-1H-indol-3-yl)ethan-1-aminium；(S)-2-Amino-3-(7-(trifluoromethyl)-1H-indol-3-yl)propanoic acid；(2S)-2-amino-3-[7-(trifluoromethyl)-1H-indol-3-yl]propanoic acid
• CAS: 143266-28-8
• 化学式: C₁₂H₁₁F₃N₂O₂
• 分子量: 272.227
• InChiKey: XEWNAIZKFBMBSZ-VIFPVBQESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.2
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  79.1
• 氢给体数：
  3
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3-甲基丁-2-烯基膦酰磷酸氢酯 、 L-7-(trifluoromethyl)tryptophan 在 甘油 、 2-巯基乙醇 作用下， 反应 0.17h， 生成 7-(trifluoromethyl)-4-(dimethylallyl)tryptophan
  参考文献：
  名称：

  Dimethylallyltryptophan synthase. An enzyme-catalyzed electrophilic aromatic substitution

  摘要：

  Dimethylallyltryptophan (DMAT) synthase catalyzes the alkylation of L-tryptophan at C(4) by dimethylallyl diphosphate (DMAPP) in the first pathway-specific step in the biosynthesis of ergot alkaloids. The mechanism of the reaction was studied with analogs of both substrates. Five 7-substituted derivatives of N-acetyltryptophan (2, Z = OCH3, CH3, F, CF3, and NO2) were synthesized. The L enantiomers of the free amino acids were obtained by selective hydrolysis of the racemate using aminoacylase from Aspergillus. In addition, the E and Z fluoromethyl and difluoromethyl analogs of DMAPP (1, Y = CH3, CH2F, CHF2) were prepared. Rates of the enzyme-catalyzed reactions were measured for the dimethylallyl derivatives with L-tryptophan and for the L-tryptophan derivatives with DMAPP. In addition, the relative reactivities of the methanesulfonate derivatives of the DMAPP analogs were determined for solvolysis in aqueous acetone. A Hammett plot for the tryptophan analogs gave a good linear correlation with rho = -2.0. In addition, a Hammett plot of the logarithms of the relative rates of solvolysis and enzyme-catalyzed alkylation gave a positive linear correlation. These results indicate that the prenyl-transfer reaction catalyzed by DMAT synthase is an electrophilic aromatic substitution and is mechanistically similar to the electrophilic alkylation catalyzed by farnesyl diphosphate synthase.

  DOI：

  10.1021/ja00045a004
• 作为产物：
  描述：

  3-(1-Acetyl-7-trifluoromethyl-1H-indol-3-yl)-2-amino-propionic acid 生成 L-7-(trifluoromethyl)tryptophan
  参考文献：
  名称：

  Dimethylallyltryptophan synthase. An enzyme-catalyzed electrophilic aromatic substitution

  摘要：

  Dimethylallyltryptophan (DMAT) synthase catalyzes the alkylation of L-tryptophan at C(4) by dimethylallyl diphosphate (DMAPP) in the first pathway-specific step in the biosynthesis of ergot alkaloids. The mechanism of the reaction was studied with analogs of both substrates. Five 7-substituted derivatives of N-acetyltryptophan (2, Z = OCH3, CH3, F, CF3, and NO2) were synthesized. The L enantiomers of the free amino acids were obtained by selective hydrolysis of the racemate using aminoacylase from Aspergillus. In addition, the E and Z fluoromethyl and difluoromethyl analogs of DMAPP (1, Y = CH3, CH2F, CHF2) were prepared. Rates of the enzyme-catalyzed reactions were measured for the dimethylallyl derivatives with L-tryptophan and for the L-tryptophan derivatives with DMAPP. In addition, the relative reactivities of the methanesulfonate derivatives of the DMAPP analogs were determined for solvolysis in aqueous acetone. A Hammett plot for the tryptophan analogs gave a good linear correlation with rho = -2.0. In addition, a Hammett plot of the logarithms of the relative rates of solvolysis and enzyme-catalyzed alkylation gave a positive linear correlation. These results indicate that the prenyl-transfer reaction catalyzed by DMAT synthase is an electrophilic aromatic substitution and is mechanistically similar to the electrophilic alkylation catalyzed by farnesyl diphosphate synthase.

  DOI：

  10.1021/ja00045a004

文献信息

• ¹⁸F-Trifluoromethanesulfinate Enables Direct C–H ¹⁸F-Trifluoromethylation of Native Aromatic Residues in Peptides
  作者：Choon Wee Kee、Osman Tack、Florian Guibbal、Thomas C. Wilson、Patrick G. Isenegger、Mateusz Imiołek、Stefan Verhoog、Michael Tilby、Giulia Boscutti、Sharon Ashworth、Juliette Chupin、Roxana Kashani、Adeline W. J. Poh、Jane K. Sosabowski、Sven Macholl、Christophe Plisson、Bart Cornelissen、Michael C. Willis、Jan Passchier、Benjamin G. Davis、Véronique Gouverneur

  DOI：10.1021/jacs.9b11709

  日期：2020.1.22

  18F labeling strategies for unmodified peptides with [18F]fluoride require 18F-labeled prosthetics for bioconjugation more often with cysteine thiols or lysine amines. Here we explore selective radical chemistry to target aromatic residues applying C–H 18F-trifluoromethylation. We report a one-step route to [18F]CF3SO2NH4 from [18F]fluoride and its application to direct [18F]CF3 incorporation at tryptophan

  用[18F]氟化物对未修饰的肽进行 18F 标记策略需要 18F 标记的假体，以便更频繁地与半胱氨酸硫醇或赖氨酸胺进行生物共轭。在这里，我们探索选择性自由基化学，以应用 C–H 18F-三氟甲基化来靶向芳香族残基。我们报告了一种从[18F]氟化物合成[18F]CF3SO2NH4的一步路线，及其使用与重组人胰岛素一样复杂的未修饰肽直接将[18F]CF3掺入色氨酸或酪氨酸残基的应用。奥曲肽[Trp(2-CF218F)]的全自动放射合成可实现体内正电子发射断层扫描成像。
• [EN] FLUORINATION METHOD<br/>[FR] PROCÉDÉ DE FLUORATION
  申请人：UNIV OXFORD INNOVATION LTD

  公开号：WO2020053596A1

  公开（公告）日：2020-03-19

  The invention relates to a process for producing a compound comprising the anion [CF2 18FSO2]-, which process comprises treating a difluorocarbene source with (i) a source of 18F- and (ii) a source of SO2. The invention relates to a compound which comprises that anion. The invention also relates to the use of the compound comprising the anion [CF2 18FSO2]- to produce a compound comprising an 18F-trifluoromethyl functionalised aromatic group. Compounds comprising an 18F-trifluoromethyl functionalised aromatic group are also the subject of the present invention.

  该发明涉及一种生产含阴离子[CF2 18FSO2]-的化合物的方法，该方法包括将二氟卡宾源与(i) 18F-源和(ii) SO2源处理。该发明涉及一种包含该阴离子的化合物。该发明还涉及利用含阴离子[CF2 18FSO2]-的化合物生产含有18F-三氟甲基官能化芳基的化合物。含有18F-三氟甲基官能化芳基的化合物也是本发明的主题。
• FLUORINATION METHOD
  申请人：Oxford University Innovation Limited

  公开号：EP3849956A1

  公开（公告）日：2021-07-21