methyl (tert-butoxycarbonyl)-L-valyl-L-tryptophanate | 41863-58-5

• 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 (tert-butoxycarbonyl)-L-valyl-L-tryptophanate
• 英文别名: Boc-Val-Trp-OMe；methyl (2S)-3-(1H-indol-3-yl)-2-[[(2S)-3-methyl-2-[(2-methylpropan-2-yl)oxycarbonylamino]butanoyl]amino]propanoate
• CAS: 41863-58-5
• 化学式: C₂₂H₃₁N₃O₅
• 分子量: 417.505
• InChiKey: AIHJFGQZJBMYEB-ROUUACIJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  30
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  110
• 氢给体数：
  3
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl (tert-butoxycarbonyl)-L-valyl-L-tryptophanate 反应 7.0h， 以75%的产率得到L-valyl-L-tryptophan anhydride
  参考文献：
  名称：

  On the fate of the tryptophan stereocenter during the synthesis of hexacyclic analogues of N-acetylardeemin

  摘要：

  The reaction between 6-acetyl-3-alkyl-1-ethoxy-3,4,5a,6, 11,11a-hexahydro-10bH-pyrazino-[2 ',1 '-5,1]pyrrolo[2,3-b]indole-l,4-diones and anthranilic acid was studied from a stereochemical point of view. Various degrees of epimerization of the tryptophan and alanine stereocenters were observed in compounds with a cis relationship between their H-3 and H-11a hydrogen atoms, and stereochemistry was retained in the trans compounds. These observations are explained in terms of steric compression between the C-5=O, C-7-alkyl and C-8=O groups in the hexacyclic reaction products. Acylation at N-2 with o-azidobenzoyl chloride followed by an intramolecular aza Wittig reaction afforded the target 10-acetyl-5,7,8,9a, 10,14b, 15,15a-octahydroindolo[3 ",2 "-4 ',5 ']pyrrolo[2 ',1 '-3,4]pyrazino[2,1-b]quinazoline-5,8-diones with retention of all stereocenters. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(98)00307-3
• 作为产物：
  描述：

  L-色氨酸甲酯盐酸盐 、 (2S)-2-[(tert-butoxycarbonyl)amino]-3-methylbutanethioic S-acid 在 caesium carbonate 、 2,4-二硝基氟苯 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 3.08h， 以76%的产率得到methyl (tert-butoxycarbonyl)-L-valyl-L-tryptophanate
  参考文献：
  名称：

  用Sanger和Mukaiyama试剂从硫代酸和胺类肽进行无差向异构的嵌段合成

  摘要：

  在游离胺存在下，由受保护氨基酸和肽衍生的C末端硫代酸与Sanger试剂和其他电子不足的芳基卤化物快速反应而形成的高活化硫酯立即与胺形成肽键。该基本无差向异构的方法用于受阻八肽的4 + 4嵌段合成（请参阅方案； Boc，Pbf和Trt是保护基）。

  DOI：

  10.1002/anie.200805782

文献信息

• Easy access to drug building-blocks through benzylic C–H functionalization of phenolic ethers by photoredox catalysis
  作者：Tobias Brandhofer、Martin Stinglhamer、Volker Derdau、María Méndez、Christoph Pöverlein、Olga García Mancheño

  DOI：10.1039/d1cc01756j

  日期：——

  A visible light-mediated photocatalyzed C–C-bond forming method for the benzylic C–H functionalization of phenolether containing synthetic building blocks based on a radical-cation/deprotonation strategy is reported. This method allows the mild, selective generation of benzyl radicals in phenolic complex molecules and drug-like compounds, providing new entries in synthetic and medicinal chemistry.

  报道了一种基于自由基阳离子/去质子化策略的可见光介导的光催化 C - C 键形成方法，用于含合成结构单元的苯酚醚的苄基 C-H 官能化。该方法允许在酚类复合物分子和类药物化合物中温和、选择性地生成苄基，为合成和药物化学提供了新的入口。
• Post-synthetic functionalization of tryptophan protected peptide sequences through indole (C-2) photocatalytic alkylation
  作者：Rafaely N. Lima、José A. C. Delgado、Darlon I. Bernardi、Roberto G. S. Berlinck、Nikolaos Kaplaneris、Lutz Ackermann、Márcio W. Paixão

  DOI：10.1039/d1cc01822a

  日期：——

  report a selective, mild, and efficient C–H functionalization of tryptophan and tryptophan-containing peptides with activated α-bromo-carbonyl compounds under visible-light irradiation. The protocol efficiency is outlined by the wide substrate scope and excellent tolerance of sensitive functional groups present in the amino acid side chains. The method can be successfully extended to access pharmaco-peptide

  我们报告了在可见光照射下用活化的 α-溴-羰基化合物对色氨酸和含色氨酸的肽进行选择性、温和和有效的 C-H 功能化。该协议的效率由广泛的底物范围和氨基酸侧链中存在的敏感官能团的出色耐受性概述。该方法可以成功扩展到访问药物肽缀合物支架。
• Catalytic C2 prenylation of unprotected indoles: Late-stage diversification of peptides and two-step total synthesis of tryprostatin B
  作者：Yan-Cheng Hu、Ying Li、Ding-Wei Ji、Heng Liu、Hao Zheng、Gong Zhang、Qing-An Chen

  DOI：10.1016/s1872-2067(20)63780-9

  日期：2021.9

  C3 prenylation/migration pathways are engaged in the reaction. Notably, this practical strategy can be applied to the late-stage diversification of tryptophan-based peptides and concise synthesis of tryprostatin B.

  C 2烯丙基化的吲哚广泛存在于各种生物活性天然生物碱中。因此，将异戊二烯基选择性地安装在NH吲哚的C 2位置上具有重要意义。然而，已知的方案通常需要多步程序和化学计量的促进剂。在本文中，我们开发了通过酸催化使廉价的叔戊烯基醇对NH吲哚进行一步一步C2烯丙基化。其显着特征包括良好的区域选择性，阶跃和原子经济性，广泛的底物范围以及简单的催化体系。机理研究表明，C2异戊二烯化和C3异戊二烯化/迁移途径均参与了反应。值得注意的是，该实用策略可应用于色氨酸基肽的后期多样化和Tryprostatin B的简明合成。
• Late‐Stage Halogenation of Peptides, Drugs and (Hetero)aromatic Compounds with a Nucleophilic Hydrazide Catalyst
  作者：Haripriyo Mondal、Subimal Patra、Shuvendu Saha、Tarak Nayak、Uddalak Sengupta、Modhu Sudan Maji

  DOI：10.1002/anie.202312597

  日期：2023.12.18

  A hydrazide catalyst is introduced for the late-stage halogenation of peptides, drugs and (hetero)aromatics with high efficiency and selectivity. The active site comprises the hydrazide group attached to a sulfonamide moiety, which facilitates the acceptance as well as delivery of halonium species from the N-halosuccinimide source to the substrates, thus featuring a cooperative interaction.

  引入酰肼催化剂，用于高效、选择性地对肽、药物和（杂）芳族化合物进行后期卤化。活性位点包含连接到磺酰胺部分的酰肼基团，这有利于卤鎓物质从N-卤代琥珀酰亚胺源到底物的接受和递送，从而具有协同相互作用的特征。
• Direct Fluorosulfonamidation of (Hetero)arenes and Alkenes with Photoredox-Active Fluorosulfamoyl Radical Reagents
  作者：Ting Xiong、Qi-Long Chen、Zi-Yan Zhang、Gui Lu、Jiang Weng

  DOI：10.1021/acscatal.4c03550

  日期：2024.8.16

  Sulfur(VI) fluoride exchange (SuFEx) is a second-generation click chemistry reaction that relies on the unique reactivities of SVI–F bonds. The development of efficient methods for incorporating a S(VI)–F motif into molecules is of great significance. Sulfamoyl fluorides (R1R2NSO2F), serving as versatile SuFExable hubs, are typically synthesized by using “+SO2F” reagents to establish N-SO2F bonds.

  硫 (VI) 氟化物交换 (SuFEx) 是第二代点击化学反应，依赖于 S VI –F 键的独特反应性。开发将 S(VI)-F 基序整合到分子中的有效方法具有重要意义。磺胺酰氟(R 1 R 2 NSO 2 F)作为多功能SuFExable中心，通常通过使用“ + SO 2 F”试剂建立N-SO 2 F键来合成。在这项研究中，我们报告了N-氟氨磺酰吡啶盐 (NFSAP) 作为自由基氟磺酰胺化试剂的开发，该试剂易于获得且实验室稳定。通过使用NFSAP作为重要的氟氨磺酰基自由基(•NSO 2 F)前体，通过不同的C-N键形成反应将NSO 2 F基团直接安装到（杂）芳烃和烯烃上。该平台有助于在温和的光催化条件下集体合成高功能化的N-芳基、 N-烷基和N-烯基氨磺酰氟(R 1 R 2 NSO 2 F)，并已应用于药物和多肽的后期功能化。