cyclo(β-HGlu(OBn))3 | 218943-47-6

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酰胺类
• 英文名称: cyclo(β-HGlu(OBn))3
• 英文别名: benzyl 3-[(2S,6S,10S)-4,8,12-trioxo-6,10-bis(3-oxo-3-phenylmethoxypropyl)-1,5,9-triazacyclododec-2-yl]propanoate
• CAS: 218943-47-6
• 化学式: C₃₉H₄₅N₃O₉
• 分子量: 699.801
• InChiKey: CXJVOQBTVNBPRQ-ZDCRTTOTSA-N

物化性质

• 沸点：
  913.7±65.0 °C(Predicted)
• 密度：
  1.176±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  51
• 可旋转键数：
  18
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  166
• 氢给体数：
  3
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  cyclo(β-HGlu(OBn))3 在 palladium on activated charcoal 氢气 、 lithium chloride 作用下， 以 四氢呋喃 为溶剂， 以29%的产率得到3-[(2S,6S,10S)-6,10-Bis-(2-carboxy-ethyl)-4,8,12-trioxo-1,5,9-triaza-cyclododec-2-yl]-propionic acid
  参考文献：
  名称：

  Preparation and NMR Structure of the Cyclo-β-tripeptide [β3-HGlu]3 in Aqueous Solution: A New Class of Enterobactin-TypeC3-Symmetrical Ligands?, Preliminary Communication

  摘要：

  To date, cyclo-beta-tripeptides (twelve-membered-ring trilactams, C) have resisted structural investigations because of their extreme insolubility. Modelling and comparison with the corresponding tetramers indicate that the rings stack to form tube-like hydrogen-bonded aggregates (D). By exploiting the solubilizing effect of LiCl on peptides in THF, we were able to prepare the water-soluble title compound and determine its structure (E) by NMR spectroscopy. Structural similarities and differences between the trilactam ring of [beta(3)-HGlu](3) and the corresponding trilactone ring, such as that of enterobactin (A), are discussed, and structures ('elongated'; F, G) are proposed that should be able to serve as tridentate or trivalent ligands for metal centers.

  DOI：

  10.1002/(sici)1522-2675(19990609)82:6<957::aid-hlca957>3.0.co;2-h
• 作为产物：
  描述：

  (S)-5-(benzyloxy)-2-((tert-butoxycarbonyl)amino)-5-oxopentanoic (ethyl carbonic) anhydride 在 水 、 silver trifluoroacetate 、 1-羟基苯并三唑 、 溶剂黄146 、 1-(3-二甲基氨基丙基)-3-乙基碳二亚胺 、 三乙胺 、 N,N-二异丙基乙胺 、 锌 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 乙腈 为溶剂， 反应 56.5h， 生成 cyclo(β-HGlu(OBn))3
  参考文献：
  名称：

  Linear and cyclic β3-oligopeptides with functionalised side-chains (-CH2OBn, -CO2Bn, -CH2CH2CO2Bn) derived from serine and from aspartic and glutamic acid

  摘要：

  天然的β-氨基酸衍生物Boc-Asp(β-OH)-OBn，以及Boc-β-HGlu(OBn)-OH和Boc-β-HSer(OBn)-OH（分别通过Arndt-Eistert同系化法从适当保护的谷氨酸和丝氨酸制备），被用作合成由2到6个β-氨基酸组成的线性（11-20）和环状（21-23）β-寡肽的构建模块[使用三氯乙基（TCE）酯基团进行C端保护和五氟苯酯激活进行大环化]。尽管线性衍生物在溶液中足以用于反应和结构研究，但环状β-三肽和六肽则不然（根据FT-IR测量，它们形成了氢键网络，可能是由所谓的纳米管组成）。Boc-OTCE保护的六肽（19）和无保护的六肽（20）[β-Asp(OBn)-β-HGlu(OBn)-β-HSer(OBn)]2的CD光谱存在显著差异，只有无保护形式在210到220 nm之间显示熟悉的负Cotton效应模式（表明为314螺旋）。在甲醇中对自由末端的六肽20进行NMR分析揭示了存在一个中心、左旋的螺旋转弯（14元氢键环）。结果进行了讨论并与先前获得的具有非功能化侧链的类似β-肽的结果进行了比较。

  DOI：

  10.1039/a805478i

文献信息

• Linear and cyclic β3-oligopeptides with functionalised side-chains (-CH2OBn, -CO2Bn, -CH2CH2CO2Bn) derived from serine and from aspartic and glutamic acid
  作者：Jennifer L. Matthews、Karl Gademann、Bernhard Jaun、Dieter Seebach

  DOI：10.1039/a805478i

  日期：——

  The natural β-amino acid derivative Boc-Asp(β-OH)-OBn, as well as Boc-β-HGlu(OBn)-OH and Boc-β-HSer(OBn)-OH (prepared from appropriately protected glutamic acid and serine, respectively, by Arndt–Eistert homologation), were employed as building blocks for the synthesis of linear (11–20) and cyclic (21–23) β-oligopeptides consisting of two to six β-amino acids [using trichloroethyl (TCE) ester groups for C-terminal protection and pentafluorophenyl-ester activation for macrocyclisation]. While the linear derivatives are soluble enough for reactions and structural investigations in solution, the cyclo-β-tri- and -hexapeptides are not (according to FT-IR measurements they form networks of hydrogen bonds, perhaps consisting of so-called nanotubes). The CD spectra of the Boc–OTCE-protected (19) and of the unprotected (20) β-hexapeptides [β-Asp(OBn)-β-HGlu(OBn)-β-HSer(OBn)]2 differ drastically, and only the unprotected form shows the familiar pattern of a negative Cotton effect between 210 and 220 nm (indicative of a 314 helix). An NMR analysis in methanol of the β-hexapeptide 20 with free termini reveals the presence of a single, central, left-handed helix turn (14-membered hydrogen-bonded ring). The results are discussed and compared with those obtained previously for analogous β-peptides carrying non-functionalised side chains.

  天然的β-氨基酸衍生物Boc-Asp(β-OH)-OBn，以及Boc-β-HGlu(OBn)-OH和Boc-β-HSer(OBn)-OH（分别通过Arndt-Eistert同系化法从适当保护的谷氨酸和丝氨酸制备），被用作合成由2到6个β-氨基酸组成的线性（11-20）和环状（21-23）β-寡肽的构建模块[使用三氯乙基（TCE）酯基团进行C端保护和五氟苯酯激活进行大环化]。尽管线性衍生物在溶液中足以用于反应和结构研究，但环状β-三肽和六肽则不然（根据FT-IR测量，它们形成了氢键网络，可能是由所谓的纳米管组成）。Boc-OTCE保护的六肽（19）和无保护的六肽（20）[β-Asp(OBn)-β-HGlu(OBn)-β-HSer(OBn)]2的CD光谱存在显著差异，只有无保护形式在210到220 nm之间显示熟悉的负Cotton效应模式（表明为314螺旋）。在甲醇中对自由末端的六肽20进行NMR分析揭示了存在一个中心、左旋的螺旋转弯（14元氢键环）。结果进行了讨论并与先前获得的具有非功能化侧链的类似β-肽的结果进行了比较。
• Preparation and NMR Structure of the Cyclo-β-tripeptide [β3-HGlu]3 in Aqueous Solution: A New Class of Enterobactin-TypeC3-Symmetrical Ligands?, Preliminary Communication
  作者：Karl Gademann、Dieter Seebach

  DOI：10.1002/(sici)1522-2675(19990609)82:6<957::aid-hlca957>3.0.co;2-h

  日期：1999.6.9

  To date, cyclo-beta-tripeptides (twelve-membered-ring trilactams, C) have resisted structural investigations because of their extreme insolubility. Modelling and comparison with the corresponding tetramers indicate that the rings stack to form tube-like hydrogen-bonded aggregates (D). By exploiting the solubilizing effect of LiCl on peptides in THF, we were able to prepare the water-soluble title compound and determine its structure (E) by NMR spectroscopy. Structural similarities and differences between the trilactam ring of [beta(3)-HGlu](3) and the corresponding trilactone ring, such as that of enterobactin (A), are discussed, and structures ('elongated'; F, G) are proposed that should be able to serve as tridentate or trivalent ligands for metal centers.