维格列汀杂质 | 19943-27-2

• 物质功能分类: 分析化学 - 标准品 - 药典标准品和杂质标准品
• 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
• 中文名称: 维格列汀杂质
• 英文名称: (5aS,10aS)-octahydrodipyrrolo[1,2-a:1',2'-d]pyrazine-5,10-dione
• 英文别名: cyclo(-L-Pro-L-Pro-)；cyclo(Pro-Pro)；(3S,6S)-1,6-3,4-bis(propylidene)-1,4-piperazine-2,5-dione；(S,S)-octahydrodipyrrolo[1,2-a:1',2'-d]pyrazine-5,10-dione；(3S,9S)-1,7-Diazatricyclo[7.3.0.03,7]dodecane-2,8-dione
• CAS: 19943-27-2
• 化学式: C₁₀H₁₄N₂O₂
• 分子量: 194.233
• InChiKey: BKASXWPLSXFART-YUMQZZPRSA-N

物化性质

• 熔点：
  240 °C
• 沸点：
  413.5±25.0 °C(Predicted)
• 密度：
  1.32±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  40.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  维格列汀杂质 在 sodium hydroxide 、 盐酸 作用下， 以 水 为溶剂， 反应 24.0h， 以73%的产率得到L-prolyl-L-proline
  参考文献：
  名称：

  Synthesis of Prolylproline

  摘要：

  Prolylproline has been synthesized by both classical peptide synthesis method utilizing tert-butoxycarbonyl or trifluoroacetyl protection of the NH group and carbodiimide-promoted peptide bond formation and by opening of the dioxopiperazine ring in octahydrodipyrrolo[1,2-a:1 ',2 '-d]pyrazine-5,10-dione obtained by thermolysis of proline methyl ester.

  DOI：

  10.1134/s1070428019070169
• 作为产物：
  描述：

  L-脯氨酸甲酯盐酸盐 在 potassium carbonate 作用下， 生成 维格列汀杂质
  参考文献：
  名称：

  手性叔胺/L-脯氨酸共催化的对映选择性 Morita-Baylis-Hillman (MBH) 反应

  摘要：

  从容易获得的手性来源开始，已经合成了四种类型的手性胺。已发现这些手性胺与 L-脯氨酸结合是甲基乙烯基酮 (MVK) 和芳香醛之间不对称 Morita-Baylis-Hillman (MBH) 反应的有效助催化剂。相应的加合物以合理的化学产率和良好的对映选择性（高达 83% ee）形成。此外，与手性胺 4 和 L-脯氨酸的两种对映异构体的平行共催化反应表明，脯氨酸立体化学决定了新形成的手性中心的构型。此外，胺4a中游离羟基的存在提高了反应的对映选择性。基于这些发现，已经提出了这种助催化 MBH 反应的合理机制。

  DOI：

  10.1002/ejoc.200700794

文献信息

• Selective hydrogenation of primary amides and cyclic di-peptides under Ru-catalysis
  作者：Murugan Subaramanian、Ganesan Sivakumar、Jessin K. Babu、Ekambaram Balaraman

  DOI：10.1039/d0cc04550k

  日期：——

  A ruthenium(II)-catalyzed selective hydrogenation of challenging primary amides and cyclic di-peptides to their corresponding primary alcohols and amino alcohols, respectively, is reported. The hydrogenation reaction operates under mild and eco-benign conditions and can be scaled-up.

  报道了钌（II）催化的具有挑战性的伯酰胺和环状二肽分别选择性氢化为其相应的伯醇和氨基醇。氢化反应在温和的生态友好条件下进行，并且可以扩大规模。
• Altering the Sex Pheromone Cyclo(l-Pro-l-Pro) of the Diatom Seminavis robusta towards a Chemical Probe
  作者：Eli Bonneure、Amber De Baets、Sam De Decker、Koen Van den Berge、Lieven Clement、Wim Vyverman、Sven Mangelinckx

  DOI：10.3390/ijms22031037

  日期：——

  As a major group of algae, diatoms are responsible for a substantial part of the primary production on the planet. Pennate diatoms have a predominantly benthic lifestyle and are the most species-rich diatom group, with members of the raphid clades being motile and generally having heterothallic sexual reproduction. It was recently shown that the model species Seminavis robusta uses multiple sexual cues during mating, including cyclo(l-Pro-l-Pro) as an attraction pheromone. Elaboration of the pheromone-detection system is a key aspect in elucidating pennate diatom life-cycle regulation that could yield novel fundamental insights into diatom speciation. This study reports the synthesis and bio-evaluation of seven novel pheromone analogs containing small structural alterations to the cyclo(l-Pro-l-Pro) pheromone. Toxicity, attraction, and interference assays were applied to assess their potential activity as a pheromone. Most of our analogs show a moderate-to-good bioactivity and low-to-no phytotoxicity. The pheromone activity of azide- and diazirine-containing analogs was unaffected and induced a similar mating behavior as the natural pheromone. These results demonstrate that the introduction of confined structural modifications can be used to develop a chemical probe based on the diazirine- and/or azide-containing analogs to study the pheromone-detection system of S. robusta.

  作为藻类的一个主要群体，硅藻对地球上的初级生产负有重要责任。羽毛硅藻主要生活在底栖环境中，是种类最丰富的硅藻群体，其中拉菲德类成员具有运动能力，通常进行异配子性繁殖。最近的研究表明，模式物种Seminavis robusta在交配过程中使用多种性引诱物质，包括环状(l-Pro-l-Pro)作为一种吸引素。详细研究引诱物质检测系统是阐明羽毛硅藻生命周期调控的关键方面，可能为硅藻物种形成提供新的基础见解。本研究报告了合成和生物评价七种含有对环状(l-Pro-l-Pro)引诱物质进行小结构改变的新型引诱物质类似物。毒性、吸引力和干扰实验被应用来评估它们作为引诱物质的潜在活性。我们大部分的类似物显示出中等至良好的生物活性和低至无植物毒性。含有叠氮基和二氮烯基的类似物的引诱物质活性不受影响，并诱导了与天然引诱物质相似的交配行为。这些结果表明，引入有限的结构修饰可以用于开发基于叠氮基和/或二氮烯基类似物的化学探针，以研究S. robusta的引诱物质检测系统。
• Facile Synthesis of Cyclic Dipeptides and Detection of Racemization
  作者：Toshihisa Ueda、Morinobu Saito、Tetsuo Kato、Nobuo Izumiya

  DOI：10.1246/bcsj.56.568

  日期：1983.2

  Several cyclic dipeptides were synthesized by refluxing methanolic solution of dipeptide methyl esters in high yield and purity. Cyclic dipeptides prepared by the Fischer method, the Nitecki method, and the present methanol-reflux method were compared with respect to yield and optical purity. The methanol-reflux method usually gave good results. High-performance liquid chromatography was effectively applied to detect racemization.

  通过回流二肽甲酯的甲醇溶液，合成了几个高产率和高纯度的环状二肽。通过Fischer法、Nitecki法和当前的甲醇回流法准备的环状二肽，在产率和光学纯度方面进行了比较。甲醇回流法通常能得到良好的结果。高效液相色谱法有效地应用于检测外消旋化。
• Synthesis of Optically Active <b><i>C</i></b>-Allylglycine Derivatives and Conversion into Isoquinolones
  作者：Udo Nubbemeyer、Nong Zhang

  DOI：10.1055/s-2002-19804

  日期：——

  synthesized via an auxiliary controlled diastereoselective aza-Claisen rearrangement. The stereodirecting unit is placed on an auxiliary derived from commercially available (S)-proline. After N-allylation. the obtained optically active allylamines were reacted with various N-protected glycyl fluorides to give the (2R)-C-allylglycyl amides in good yields. The diastereoselectivity of the asymmetric allylation

  C-烯丙基甘氨酰胺可以通过辅助控制的非对映选择性氮杂-克莱森重排有效合成。立体定向单元放置在衍生自市售 (S)-脯氨酸的辅助物上。N-烯丙基化后。获得的光学活性烯丙胺与各种N-保护的甘氨酰氟反应以良好的收率得到(2R)-C-烯丙基甘氨酰胺。不对称烯丙基化的非对映选择性在 1:1 和 >1:15 之间变化，具体取决于 N-保护基团、助剂和反应温度。同样，C-烯丙基甘氨酸衍生物可用作肽合成中的单体以合成(R)-脯氨酸衍生物或手性异喹诺酮类；后者应作为生物碱总合成的组成部分。
• Towards a General Understanding of Carbonyl-Stabilised Ammonium Ylide-Mediated Epoxidation Reactions
  作者：Johanna Novacek、Lukas Roiser、Katharina Zielke、Raphaël Robiette、Mario Waser

  DOI：10.1002/chem.201602052

  日期：2016.8.1

  carbonyl‐stabilised ammonium ylide‐mediated epoxidation reactions were systematically investigated by experimental and computational means and the hereby obtained energy profiles provide explanations for the observed experimental results. In addition, we were able to identify the first tertiary amine‐based chiral auxiliary that allows for high enantioselectivities and high yields for such epoxidation reactions.

  通过实验和计算手段系统地研究了羰基稳定的铵叶立德介导的环氧化反应的关键因素，由此获得的能量分布为观察到的实验结果提供了解释。此外，我们还能够鉴定出第一个基于叔胺的手性助剂，该助剂可实现高对映选择性和高产率，用于此类环氧化反应。