L-valyl-L-tryptophan anhydride | 29552-08-7

• 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: L-valyl-L-tryptophan anhydride
• 英文别名: polanrazine A；Polanrazine A；(3S,6S)-3-(1H-indol-3-ylmethyl)-6-propan-2-ylpiperazine-2,5-dione
• CAS: 29552-08-7
• 化学式: C₁₆H₁₉N₃O₂
• 分子量: 285.346
• InChiKey: WNWCQIPRIITCPM-KBPBESRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  74
• 氢给体数：
  3
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  L-valyl-L-tryptophan anhydride 在 吡啶 、 三氟乙酸 作用下， 反应 3.03h， 生成 (3S,5aR,10bS,11aS)-6-acetyl-3-isopropyl-1,3,4,5a,6,10b,11,11a-octahydro-2H-pyrazino<2',1'-5,1>pyrrolo<2,3-b>indole-1,4-dione
  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 在 钯 氨 、 氢气 、 N,N'-二环己基碳二亚胺 作用下， 以 甲醇 为溶剂， 生成 L-valyl-L-tryptophan anhydride
  参考文献：
  名称：

  Conformational effects in reversed-phase liquid chromatographic separation of diastereomers of cyclic dipeptides

  摘要：

  The capacity factors, k', of 11 cyclic dipeptides (X-Y) including diastereomers have been determined on an RP-HPLC column in 30% and 50% methanol and 10%, 30%, and 50% acetonitrile solutions. These factors are roughly correlated with hydrophobic parameters, such as octanol-water partition coefficients estimated and k' values for alcohols. For a pair of diastereomers of cyclic (L-X-L-Phe) and (L-X-D-Phe) derivatives k'LL is larger than k'LD, and for cyclic (D-Ala-L-Trp) and (L-Ala-L-Trp) k'LL is smaller than k'DL, particularly in highly aqueous solutions. These elution orders can be well predicted by the holistic molecular surface area approach which takes into account the folded structures of cyclic dipeptides. The present results will be useful for prediction of the log k' values of larger peptides and the hydrophobicity and related properties of peptides.

  DOI：

  10.1021/ac00062a010

文献信息

• Copper-Catalyzed Diastereoselective Arylation of Tryptophan Derivatives: Total Synthesis of (+)-Naseseazines A and B
  作者：Madeleine E. Kieffer、Kangway V. Chuang、Sarah E. Reisman

  DOI：10.1021/ja4023557

  日期：2013.4.17

  A copper-catalyzed arylation of tryptophan derivatives is reported. The reaction proceeds with high site- and diastereoselectivity to provide aryl pyrroloindoline products in one step from simple starting materials. The utility of this transformation is highlighted in the five-step syntheses of the natural products (+)-naseseazine A and B.

  报道了色氨酸衍生物的铜催化芳基化。该反应以高位点和非对映选择性进行，从简单的起始材料一步即可提供芳基吡咯并二氢吲哚产物。这种转化的效用在天然产物 (+)-naseseazine A 和 B 的五步合成中得到了强调。
• Regioselective Palladium-Catalyzed C-H Bond Trifluoroethylation of Indoles: Exploration and Mechanistic Insight
  作者：Hao Zhang、Hao-Yang Wang、Yixin Luo、Chaohuang Chen、Yimiao Cao、Pinhong Chen、Yin-Long Guo、Yu Lan、Guosheng Liu

  DOI：10.1021/acscatal.7b03220

  日期：2018.3.2

  A selective palladium-catalyzed trifluoroethylation reaction of indoles has been developed. The C-H bond activation process, using CF3CH2I as the fluoroalkyl source, can be employed to prepare a variety of 2-CF3CH2 substituted indoles. Moreover, because it displays a wide functional group tolerance, the process can be employed to synthesize CF3CH2-containing bioactive indoles through late-stage trifluoroethylation

  已经开发了选择性钯催化的吲哚三氟乙基化反应。使用CF 3 CH 2 I作为氟代烷基源的CH键活化过程可用于制备各种2-CF 3 CH 2取代的吲哚。此外，由于它显示出宽泛的官能团耐受性，因此该方法可用于合成CF 3 CH 2。晚期三氟乙基化制备含生物活性的吲哚。初步机理研究和DFT计算的结果表明，作为离子钯配体的β-二酮通过加速氧化加成步骤，在控制钯催化的三氟乙基化反应的效率方面起着重要作用。相反，在速率确定步骤中涉及吲哚NH质子在钯中心的转移。
• Data Science-Driven Analysis of Substrate-Permissive Diketopiperazine Reverse Prenyltransferase NotF: Applications in Protein Engineering and Cascade Biocatalytic Synthesis of (−)-Eurotiumin A
  作者：Samantha P. Kelly、Vikram V. Shende、Autumn R. Flynn、Qingyun Dan、Ying Ye、Janet L. Smith、Sachiko Tsukamoto、Matthew S. Sigman、David H. Sherman

  DOI：10.1021/jacs.2c06631

  日期：2022.10.26

  functionalization prevalent in the biosynthesis of a diverse array of biologically active bacterial, fungal, plant, and metazoan diketopiperazine (DKP) alkaloids. Toward the development of a unified strategy for biocatalytic construction of prenylated DKP indole alkaloids, we sought to identify and characterize a substrate-permissive C2 reverse prenyltransferase (PT). As the first tailoring event within the biosynthesis

  异戊二烯转移是一种早期碳氢键 (C–H) 功能化，普遍存在于多种具有生物活性的细菌、真菌、植物和后生动物二酮哌嗪 (DKP) 生物碱的生物合成中。为了开发异戊二烯化 DKP 吲哚生物碱生物催化构建的统一策略，我们试图鉴定和表征底物允许的 C2 反向异戊二烯基转移酶 (PT)。作为细胞毒性诺托酰胺代谢物生物合成中的第一个剪裁事件，PT NotF 催化短维胺 F 的 C2 反向异戊烯转移。解析 NotF 的晶体结构（与天然底物和异戊烯供体模拟物二甲基烯丙基 S-硫代二磷酸 (DMSPP) 形成复合物）揭示了一个大的，暴露于溶剂的活性位点，提示 NotF 可能具有非常广泛的底物范围。为了评估 NotF 的底物选择性，我们合成了一组 30 种空间和电子分化的色氨酸 DKP，其中大部分在合成有用的转化（2 至 >99%）中被 NotF 选择性异戊二烯化。该底物库的定量表示和描述性统计模型的开发提供了对
• Iron‐Catalyzed Biomimetic Dimerization of Tryptophan‐Containing Peptides
  作者：Hirofumi Ueda、Soichiro Sato、Kenta Noda、Hiroyuki Hakamata、Eunsang Kwon、Nagao Kobayashi、Hidetoshi Tokuyama

  DOI：10.1002/anie.202302404

  日期：——

  Biomimetic oxidative dimerization of tryptophan derivatives catalyzed by an iron octacarboxy phthalocyanine complex was established in aqueous media with oxygen as a bulk oxidant. This protocol allows the dimerization of a wide range of tryptophan-containing peptides with remarkable functional-group tolerance to construct natural and unnatural pyrroloindole dimers and dimerized peptides with a unique

  八羧基酞菁铁络合物催化的色氨酸衍生物的仿生氧化二聚反应是在水性介质中以氧作为本体氧化剂建立的。该协议允许对具有显着功能组耐受性的各种含色氨酸肽进行二聚化，以构建天然和非天然的吡咯并吲哚二聚体和二聚化肽，并具有连接两个转弯结构的独特支架。
• Late‐stage C−H Functionalization of Tryptophan‐Containing Peptides with Thianthrenium Salts: Conjugation and Ligation
  作者：Nikolaos Kaplaneris、Alejandro Puet、Felix Kallert、Julia Pöhlmann、Lutz Ackermann

  DOI：10.1002/anie.202216661

  日期：2023.2.20

  Palladium-catalyzed C−H arylation of tryptophan-containing peptides with readily accessible and modular arylthianthrenium salts was investigated. The modular nature of this arylating agent allowed the expedient stitching of tryptophan-containing peptides with drug, natural product, and peptidic scaffolds by forging sterically congested biaryl linkages.

  研究了钯催化的含色氨酸肽的 C-H 芳基化与易于获得和模块化的芳基噻蒽盐。这种芳基化剂的模块化性质允许通过形成空间拥挤的双芳基连接，方便地将含有色氨酸的肽与药物、天然产物和肽支架拼接起来。