methyl (S)-2-((tert-butoxycarbonyl)amino)-5-oxo-5-phenylpentanoate | 1611470-49-5

• 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 (S)-2-((tert-butoxycarbonyl)amino)-5-oxo-5-phenylpentanoate
• 英文别名: (S)-Methyl 2-((tert-butoxycarbonyl)amino)-5-oxo-5-phenylpentanoate；methyl (2S)-2-[(2-methylpropan-2-yl)oxycarbonylamino]-5-oxo-5-phenylpentanoate
• CAS: 1611470-49-5
• 化学式: C₁₇H₂₃NO₅
• 分子量: 321.373
• InChiKey: WEYIBENIWMZWQA-ZDUSSCGKSA-N

物化性质

• 沸点：
  467.5±40.0 °C(Predicted)
• 密度：
  1.124±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  23
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  81.7
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl (S)-2-((tert-butoxycarbonyl)amino)-5-oxo-5-phenylpentanoate 在 palladium on activated charcoal 、 水 、 氢气 、 三氟乙酸 、 sodium hydroxide 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 19.0h， 生成
  参考文献：
  名称：

  Prolinyl Phosphoramidates of Nucleotides with Increased Reactivity

  摘要：

  Nucleoside monophosphates (NMPs) are the subunits of RNA. They are incorporated into growing complementary strands when sequences are copied in enzyme‐free reactions using organic leaving groups at the phosphates. Amino acids are rarely considered as leaving groups, but proline can act as a leaving group when N‐linked to NMPs, so that prolinyl NMPs hydrolyze in aqueous buffer at 37 °C, with half‐life times as short as 2.4 h, and they act as monomers in enzyme‐free primer extension. Still, their level of reactivity is insufficient for practical purposes, requiring months for some extensions. Herein we report the synthesis of eight substituted prolinyl AMPs together with seven related compounds and the results of a study of their reactivity. A δ‐carboxy prolinyl NMP was found to be converted with a half‐life time of just 11 min in magnesium‐free buffer, and a δ‐isopropyl prolinyl NMP was shown to react sevenfold faster than its prolinyl counterpart in enzyme‐free genetic copying of RNA. Our results indicate that both anchimeric and steric effects can be employed to increase the reactivity of aminoacidyl nucleotides, i.e. compounds that combine two fundamental classes of biomolecules in one functional entity.

  DOI：

  10.1002/anie.202319958
• 作为产物：
  描述：

  L-焦谷氨酸甲酯 在 4-二甲氨基吡啶 、 碘 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 72.0h， 生成 methyl (S)-2-((tert-butoxycarbonyl)amino)-5-oxo-5-phenylpentanoate
  参考文献：
  名称：

  分子内烷基化方法合成双环和三环手性胍盐

  摘要：

  描述了导致三种新型手性胍支架的合成研究。感兴趣的结构包括在胍核心周围具有各种取代模式的双环胍衍生物，以及高度刚性的三环支架。通过应用汞 (II) 促进的 N-Boc 取代硫脲的鸟苷酸化和 Ishikawa 的脱硫环化来获得具有挑战性的目标。除了我们的合成逻辑之外，还介绍了三环胍盐的可扩展合成。

  DOI：

  10.1002/ejoc.201601154

文献信息

• (2<i>S</i>,5<i>R</i>)-2-Methylaminomethyl-1-methyl-5-phenylpyrrolidine, a chiral diamine ligand for copper(<scp>ii</scp>)-catalysed Henry reactions with superb enantiocontrol
  作者：Dagmar Scharnagel、Felix Prause、Johannes Kaldun、Robert G. Haase、Matthias Breuning

  DOI：10.1039/c4cc02429j

  日期：——

  Copper(ii)-complexes of a cis-2-aminomethyl-5-phenylpyrrolidine catalyse enantioselective Henry reactions with extraordinarily high stereocontrol.

  铜(II)配合物与顺式-2-氨基甲基-5-苯基吡咯烷催化了具有极高立体控制性的对映选择性亨利反应。
• LADA strategy for the synthesis of unnatural amino acids and direct modifications of peptides
  作者：Jun-Liang Zhou、Yun-Qi Liu、Zhan-Kui Sun

  DOI：10.1007/s11426-023-1605-2

  日期：2023.6

  Unnatural amino acids (UAAs) are important building blocks in organic synthesis and drug discovery. They are also frequently integrated into peptides or proteins for biological studies. However, the direct and simplified synthesis of UAAs remains a great challenge. At the same time, vast known peptide modifications are based on carbon-heteroatom bonds. There are no general methods for peptide modifications

  非天然氨基酸 (UAA) 是有机合成和药物发现的重要组成部分。它们还经常被整合到用于生物学研究的肽或蛋白质中。然而，UAA 的直接和简化合成仍然是一个巨大的挑战。同时，大量已知的肽修饰是基于碳-杂原子键。没有通过构建 C-C 键对肽进行修饰的通用方法。为了应对这一挑战，我们在此提出了 LADA 策略，该策略由两个步骤组成：半胱氨酸残基的选择性标记和激活，脱硫生成以碳为中心的自由基和自由基a加入烯烃以建立C-C键。这种一锅法方案具有明显的优点，例如良好的官能团耐受性、生物相容性反应条件和保留的立体化学。该策略已成功用于非天然氨基酸的合成和肽的直接修饰。
• Direct synthesis of unnatural amino acids and modifications of peptides via LADA strategy
  作者：Yunqi Liu、Junliang Zhou、Zhankui Sun

  DOI：10.1016/j.cclet.2023.108553

  日期：2024.1

  Unnatural amino acids (UAAs) have broad applications in pharmaceutical sciences and biological studies. Current synthetic methods for UAAs mainly rely on asymmetric catalysis and often require several steps. There is a lack of direct and simple methods. To address this challenge, we designed the LADA (labeling-activation-desulfurization-addition) strategy: selective labeling and activation of cysteine

  非天然氨基酸（UAA）在药物科学和生物学研究中具有广泛的应用。目前 UAA 的合成方法主要依赖于不对称催化，通常需要几个步骤。缺乏直接、简单的方法。为了应对这一挑战，我们设计了LADA（标记-活化-脱硫-加成）策略：选择性标记和活化半胱氨酸残基、光催化脱硫以及随后对烯烃进行自由基加成。虽然由两步组成，但为一锅法合成，具有官能团耐受性高、反应条件生物相容、立体化学保留等优点。这种高效的策略已成功应用于非天然氨基酸的直接合成和肽的修饰，并有超过50个实例。
• Flexible and Modular Syntheses of Enantiopure 5-cis-Substituted Prolinamines from l-Pyroglutamic Acid
  作者：Matthias Breuning、Felix Prause、Johannes Kaldun、Benjamin Arensmeyer、Benedikt Wennemann、Benjamin Fröhlich、Dagmar Scharnagel

  DOI：10.1055/s-0034-1379457

  日期：——

  A wide range (25 examples) of 5-cis-substituted prolinamines is prepared in five to ten steps starting from cheap L-pyroglutamic acid. Three routes, differing mainly in the order of introduction of the substituents at the 5-cis position, the pyrrolidine nitrogen atom, and the exocyclic amino function, are successfully developed.