(2R,3S)-2-(tert-butoxycarbonyl)-4,4,4-trifluoro-3-methylbutanoic acid | 888725-63-1

• 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: (2R,3S)-2-(tert-butoxycarbonyl)-4,4,4-trifluoro-3-methylbutanoic acid
• 英文别名: (2R,3S)-2-((tert-butoxycarbonyl)amino)-4,4,4-trifluoro-3-methylbutanoic acid；(2R,3S)-N-Boc-4,4,4-trifluorovalinol；(2R,3S)-4,4,4-trifluoro-3-methyl-2-[(2-methylpropan-2-yl)oxycarbonylamino]butanoic acid
• CAS: 888725-63-1
• 化学式: C₁₀H₁₆F₃NO₄
• 分子量: 271.237
• InChiKey: URADCGNNXPUQAP-NTSWFWBYSA-N

物化性质

• 熔点：
  85-86 °C(Solv: ligroine (8032-32-4))
• 沸点：
  331.5±42.0 °C(Predicted)
• 密度：
  1.245±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  75.6
• 氢给体数：
  2
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (2R,3S)-2-(tert-butoxycarbonyl)-4,4,4-trifluoro-3-methylbutanoic acid 在 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 以100%的产率得到(2R,3S)-4,4,4-trifluorovaline
  参考文献：
  名称：

  Indium-Mediated Diastereoselective Allylation of d- and l-Glyceraldimines with 4-Bromo-1,1,1-trifluoro-2-butene:  Highly Stereoselective Synthesis of 4,4,4-Trifluoroisoleucines and 4,4,4-Trifluorovaline

  摘要：

  A practical and efficient route for the stereoselective synthesis of (2R,3S)- and (2S,3R)-4,4,4-trifluoroisoleucines and (2R,3S)-4,4,4-trifluorovaline was developed. Indium-mediated allylation of (R)-N-benzyl-2,3-O-isopropylideneglyceraldimine 7 with 4-bromo-1,1,1-trifluoro-2-butene 4 gave the desired homoallylic amine 8 in high diastereoselectivity (> 95% de) with moderate yield. The Cbz-protected (2R,3S)-4,4,4-trifluoroisoleucine 14 and Boc-protected (2R,3S)-4,4,4-trifluorovaline 21 were then readily prepared from 8. In addition, following the same procedure, Cbz-protected (2S,3R)-4,4,4-trifluoroisoleucine 28, the enantiomer of 14, was prepared starting from (S)-N-benzyl-2,3-O-isopropylideneglyceraldimine 24.

  DOI：

  10.1021/jo0601157
• 作为产物：
  描述：

  tert-butyl (1R,2R)-1-((S)-2,2-dimethyl-1,3-dioxolan-4-yl)-3,3,3-trifluoro-2-(hydroxymethyl)propylcarbonate 在 吡啶 、 4-二甲氨基吡啶 、 ruthenium trichloride 、 sodium periodate 、 三正丁基氢锡 、 对甲苯磺酸 作用下， 以 甲醇 、 四氯化碳 、 二氯甲烷 、 水 、 xylene 为溶剂， 反应 30.0h， 生成 (2R,3S)-2-(tert-butoxycarbonyl)-4,4,4-trifluoro-3-methylbutanoic acid
  参考文献：
  名称：

  Indium-Mediated Diastereoselective Allylation of d- and l-Glyceraldimines with 4-Bromo-1,1,1-trifluoro-2-butene:  Highly Stereoselective Synthesis of 4,4,4-Trifluoroisoleucines and 4,4,4-Trifluorovaline

  摘要：

  A practical and efficient route for the stereoselective synthesis of (2R,3S)- and (2S,3R)-4,4,4-trifluoroisoleucines and (2R,3S)-4,4,4-trifluorovaline was developed. Indium-mediated allylation of (R)-N-benzyl-2,3-O-isopropylideneglyceraldimine 7 with 4-bromo-1,1,1-trifluoro-2-butene 4 gave the desired homoallylic amine 8 in high diastereoselectivity (> 95% de) with moderate yield. The Cbz-protected (2R,3S)-4,4,4-trifluoroisoleucine 14 and Boc-protected (2R,3S)-4,4,4-trifluorovaline 21 were then readily prepared from 8. In addition, following the same procedure, Cbz-protected (2S,3R)-4,4,4-trifluoroisoleucine 28, the enantiomer of 14, was prepared starting from (S)-N-benzyl-2,3-O-isopropylideneglyceraldimine 24.

  DOI：

  10.1021/jo0601157

文献信息

• Non-racemic hexafluoreleucine, and methods of making and using it
  申请人：——

  公开号：US20040138493A1

  公开（公告）日：2004-07-15

  One aspect of the invention relates to hexafluoroleucine and congeners thereof, and methods of making the compounds. Another aspect of the nvention relates to the synthesis of protein cores comprising hexafluoroleucine and congeners thereof. Certain peptides comprising hexafluorleucine and congeners thereof have been characterized using comparative biophysical studies. In general, the fluorinated peptides show higher thermal stability and enhanced resistance to chemical denaturation. Further, mixed hydrocarbonfluorocarbon cores self-sort into homogeneous bundles, suggesting new avenues for the design and manipulation of protein-protein interfaces.

  这项发明的一个方面涉及六氟亮氨酸及其同系物，以及制备这些化合物的方法。该发明的另一个方面涉及合成包含六氟亮氨酸及其同系物的蛋白质核心。通过比较生物物理学研究，已经表征了包含六氟亮氨酸及其同系物的某些肽。一般来说，氟化肽表现出更高的热稳定性和增强的抗化学变性能力。此外，混合的烃氟烃核心自我分类为均匀的束状结构，为蛋白质-蛋白质界面的设计和操纵提供了新途径。
• Conjugate hydrotrifluoromethylation of α,β-unsaturated acyl-oxazolidinones: synthesis of chiral fluorinated amino acids
  作者：Holger Erdbrink、Ilona Peuser、Ulla I. M. Gerling、Dieter Lentz、Beate Koksch、Constantin Czekelius

  DOI：10.1039/c2ob26810h

  日期：——

  A novel conjugate hydrofluoroalkylation of α,β-unsaturated acyl-oxazolidinones is described. Using this method, enantiomerically pure β-trifluoromethylated amino acids were prepared. Trifluorovaline and trifluoroisoleucine were incorporated into peptides and found to show extremely low α-helix propensities.

  描述了一种新颖的共轭氢氟烷基化α,β-不饱和酰基噁唑烷酮的方法。利用该方法，制备了手性纯的β-三氟甲基化氨基酸。三氟瓦林和三氟异亮氨酸被引入到肽中，发现其α-螺旋倾向极低。
• A Simple and Efficient Method for the Resolution of All Four Diastereomers of 4,4,4-Trifluorovaline and 5,5,5-Trifluoroleucine
  作者：Xuechao Xing、Alfio Fichera、Krishna Kumar

  DOI：10.1021/jo011097q

  日期：2002.3.1
• Indium-Mediated Diastereoselective Allylation of <scp>d</scp>- and <scp>l</scp>-Glyceraldimines with 4-Bromo-1,1,1-trifluoro-2-butene:  Highly Stereoselective Synthesis of 4,4,4-Trifluoroisoleucines and 4,4,4-Trifluorovaline
  作者：Qi Chen、Xiao-Long Qiu、Feng-Ling Qing

  DOI：10.1021/jo0601157

  日期：2006.5.1

  A practical and efficient route for the stereoselective synthesis of (2R,3S)- and (2S,3R)-4,4,4-trifluoroisoleucines and (2R,3S)-4,4,4-trifluorovaline was developed. Indium-mediated allylation of (R)-N-benzyl-2,3-O-isopropylideneglyceraldimine 7 with 4-bromo-1,1,1-trifluoro-2-butene 4 gave the desired homoallylic amine 8 in high diastereoselectivity (> 95% de) with moderate yield. The Cbz-protected (2R,3S)-4,4,4-trifluoroisoleucine 14 and Boc-protected (2R,3S)-4,4,4-trifluorovaline 21 were then readily prepared from 8. In addition, following the same procedure, Cbz-protected (2S,3R)-4,4,4-trifluoroisoleucine 28, the enantiomer of 14, was prepared starting from (S)-N-benzyl-2,3-O-isopropylideneglyceraldimine 24.