methyl (2R)-1-(2,2,2-trifluoroacetyl)pyrrolidine-2-carboxylate | 344-25-2

• 物质功能分类: 生物化工 - 常见氨基酸及蛋白质类
• 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: methyl (2R)-1-(2,2,2-trifluoroacetyl)pyrrolidine-2-carboxylate
• CAS: 344-25-2
• 化学式: C₈H₁₀F₃NO₃
• 分子量: 225.168
• InChiKey: SZHIHLKFIRSJER-RXMQYKEDSA-N

物化性质

• 熔点：
  223 °C (dec.) (lit.)
• 比旋光度：
  84.75 º (c=4, H2O)
• 沸点：
  215.41°C (rough estimate)
• 密度：
  1.36
• 溶解度：
  少量溶于甲醇和水
• LogP：
  -0.060 (est)

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  6

安全信息

• TSCA：
  Yes
• 危险品标志：
  Xn,Xi
• 安全说明：
  S24/25
• 危险类别码：
  R22
• WGK Germany：
  3
• 海关编码：
  2933990090
• 危险品运输编号：
  NONH for all modes of transport
• 危险性防范说明：
  P261,P305+P351+P338
• 危险性描述：
  H315,H319,H335

制备方法与用途

化学性质

D-脯氨酸在常温常压下为白色或浅黄色固体粉末状，具有手性中心，是一种光学活性分子。它可以旋转平面偏振光，并具有旋光度值。D-脯氨酸中的羧基和氨基都是可以离子化的反应中心，因此具有酸碱性质。在酸性条件下，它能够被质子化形成相应的正电离子；而在碱性条件下，则会去质子化形成带有负电荷的D-脯氨酸离子。该化合物结构中的羧基和氨基还能发生缩合反应，形成肽键。

应用

D-脯氨酸可用作有机合成与医药化学中间体，常用于药物分子和生物活性分子的修饰。例如，D-脯氨酸可以用于合成β-胡萝卜素，在有机合成转化中，它在酸性条件下可进行酯化反应，生成相应的氨基酯类衍生物。

合成方法

D-氨基酸是一类重要的手性试剂和中间体。目前，多数D-氨基酸是通过合成外消旋体然后拆分得到旋光异构体的方法制备的。使用不对称转化法，以(2R,3R)-酒石酸为拆分剂，在丁醛存在下进行反应，可同时使L-脯氨酸发生消旋及与(2R,3R)-酒石酸生成成盐结晶的过程。最终总收率可达82%。

生物活性

D-脯氨酸是天然氨基酸L-脯氨酸的同分异构体。

靶点

Human Endogenous Metabolite

用途

• 合成药品及食品、饲料添加剂。
• 用于β-紫罗兰叉乙醛(β-ionylideneacetaldehyde)、视黄醛(retinal) 和相关化合物的非对称自缩合反应。

反应信息

• 作为产物：
  描述：

  D-脯氨酸 在 盐酸 作用下， 以 二氯甲烷 为溶剂， 反应 0.58h， 生成 methyl (2R)-1-(2,2,2-trifluoroacetyl)pyrrolidine-2-carboxylate
  参考文献：
  名称：

  Cycloforskamide, a Cytotoxic Macrocyclic Peptide from the Sea Slug Pleurobranchus forskalii

  摘要：

  A macrocylic dodecapeptide, cycloforskamide, was isolated from the sea slug Pleurobranchus forskalii, collected off Ishigaki Island, Japan. Its planar structure was deduced by extensive NMR analyses and was further confirmed by MS/MS fragmentation analyses. Finally, the absolute configuration was determined by total hydrolysis and chiral-phase gas chromatographic analysis. This novel dodecapeptide contains three D-amino acids and three thiazoline heterocycles and exhibits cytotoxicity against murine leukemia P388 cells, with an IC50 of 5.8 mu M.

  DOI：

  10.1021/np400404r

文献信息

• Kinetic Resolution of Protected α-Amino Acid Derivatives by a Chiral <i>O</i>-Nucleophilic Acyl Transfer Catalyst
  作者：Gregory T. Notte、Tarek Sammakia

  DOI：10.1021/ja058010t

  日期：2006.4.5

  The kinetic resolution of alpha-trifluoroacetamido N-acyl oxazolidinethiones using 5-10% of the chiral, nonracemic O-nucleophilic acyl transfer catalyst 2 is described. A variety of substrates participate in this reaction in excellent yields, with s-factors ranging from 20 to 86.
• Psychrophilin E, a new cyclotripeptide, from co-fermentation of two marine alga-derived fungi of the genus <i>Aspergillus</i>
  作者：Sherif S. Ebada、Thomas Fischer、Alexandra Hamacher、Feng-Yu Du、Yoen Ok Roth、Matthias U. Kassack、Bin-Gui Wang、Eckhard H. Roth

  DOI：10.1080/14786419.2014.880911

  日期：2014.6.3

  Chemical investigation of the mycelial extract of a mixed culture of two marine alga-derived fungal strains of the genus Aspergillus has yielded one new cyclotripeptide, psychrophilin E (1), the recently reported oxepin-containing alkaloids, protuboxepin A (2) and oxepinamide E (3), together with three other polyketide derivatives (4-6). The chemical structure and relative and absolute configurations of psychrophilin E (1) were unambiguously established based on HRMS, 1D, 2D NMR and chiral-phase HPLC analysis of its hydrolysate. All the isolated compounds were assessed for their anti-proliferative activity against four different human cancer cell lines and some of them revealed selective activities.
• Cycloforskamide, a Cytotoxic Macrocyclic Peptide from the Sea Slug <i>Pleurobranchus forskalii</i>
  作者：Karen Co Tan、Toshiyuki Wakimoto、Kentaro Takada、Takashi Ohtsuki、Nahoko Uchiyama、Yukihiro Goda、Ikuro Abe

  DOI：10.1021/np400404r

  日期：2013.7.26

  A macrocylic dodecapeptide, cycloforskamide, was isolated from the sea slug Pleurobranchus forskalii, collected off Ishigaki Island, Japan. Its planar structure was deduced by extensive NMR analyses and was further confirmed by MS/MS fragmentation analyses. Finally, the absolute configuration was determined by total hydrolysis and chiral-phase gas chromatographic analysis. This novel dodecapeptide contains three D-amino acids and three thiazoline heterocycles and exhibits cytotoxicity against murine leukemia P388 cells, with an IC50 of 5.8 mu M.