-N-methyl-L-valine methyl ester | 128892-33-1

• 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: -N-methyl-L-valine methyl ester
• 英文别名: Z-D-Me-Val-L-Me-Val-OMe；Z-D-MeVal-MeVal-OMe；methyl (2S)-3-methyl-2-[methyl-[(2R)-3-methyl-2-[methyl(phenylmethoxycarbonyl)amino]butanoyl]amino]butanoate
• CAS: 128892-33-1
• 化学式: C₂₁H₃₂N₂O₅
• 分子量: 392.495
• InChiKey: XSDQERLILVFZTC-MSOLQXFVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.94
• 重原子数：
  28.0
• 可旋转键数：
  8.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  76.15
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为产物：
  描述：

  2-(N-benzyloxycarbonyl-N-methylamino)-3-methylbutyric acid methyl ester 在 palladium on activated charcoal 盐酸 、 benzotriazol-1-yloxyl-tris-(pyrrolidino)-phosphonium hexafluorophosphate 、 氢气 、 N,N-二异丙基乙胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 76.02h， 生成 -N-methyl-L-valine methyl ester
  参考文献：
  名称：

  Coupling N-Methylated Amino Acids Using PyBroP and PyCloP Halogenophosphonium Salts: Mechanism and Fields of Application

  摘要：

  PyBroP (1) and PyCloP (2), two halotripyrrolidinophosphonium hexafluorophosphates, are peptide-coupling reagents highly efficient for coupling N-methylated amino esters, in contrast with PyBOP (3), the hydroxybenzotriazolyl analogue. These halogenophosphonium salts 1 and 2 are convenient (one-pot reactions) stable solids soluble in conventional solvents. Use of them gave an excellent peptide yield with essentially no epimerization. Activation with these reagents probably involves the formation of an (acyloxy)phosphonium, as shown in the case of 2,4,6-trimethylbenzoic acid activation. In the case of reagents 1 and 2, oxazolone and/or a symmetrical anhydride were intermediates which were rapidly aminolyzed. In contrast, the benzotriazolyl ester intermediate which was formed with PyBOP (3) was poorly reactive with N-methylated amino esters. PyBroP (1) and PyCloP (2) were less efficient in the coupling of some Boc-amino acids because of N-carboxyanhydride formation; this was particularly the case when Boc-Val-OH or Boc-MeVal-OH was coupled with MeVal-OMe.

  DOI：

  10.1021/jo00088a027

文献信息

• Brop: A new reagent for coupling N-methylated amino acids
  作者：Jacques Coste、Marie-Noëlle Dufour、Antoine Pantaloni、Bertrand Castro

  DOI：10.1016/s0040-4039(00)94598-2

  日期：1990.1

  BroP (bromo tris(dimethylamino) phosphonium hexafluorophosphate) is a particularly suitable reagent for coupling N-methylated amino acids. It is stable and gives very high yields in short reaction times. Dipeptides are obtained without appreciable epimerization.

  BroP（溴化三（二甲基氨基）六氟磷酸phospho）是用于偶联N-甲基化氨基酸的特别合适的试剂。它是稳定的，并且在短的反应时间内给出了很高的产率。在没有明显差向异构的情况下获得二肽。
• A novel thiazolium type peptide coupling reagent for hindered amino acids
  作者：Peng Li、Jie Cheng Xu

  DOI：10.1016/s0040-4039(99)01763-3

  日期：1999.11

  A highly efficient coupling reagent, 2-bromo-3-ethyl-4-methyl thiazolium tetrafluoroborate (BEMT), was designed, synthesized and successfully applied to the synthesis of oligopeptides containing N-alkyl or α-C-dialkyl amino acids. Its efficiency was evaluated by HPLC and 1H NMR methods, and demonstrated by synthesis of a number of N-methyl-rich peptide segments with good yields and negligible racemization

  设计，合成了高效偶联试剂2-溴-3-乙基-4-甲基噻唑四氟硼酸酯（BEMT），并将其成功地用于合成包含N-烷基或α- C-二烷基氨基酸的寡肽。通过HPLC和1 H NMR方法评价了其效率，并通过合成了许多具有良好产率和可忽略的外消旋作用的富含N-甲基的肽段。通过HPLC，1 H NMR和IR监测研究了偶联机理。有人提出不稳定的（酰氧基）噻唑盐和N-保护的氨基酸溴化物是主要的活性中间体，伴随着N的形成-乙基-4-甲基噻唑烷酮和少量的恶唑酮和N保护的氨基酸酸酐。