2-[[2-[[(2S)-3-(4-hydroxyphenyl)-2-[[(1R,2S,6S,9R)-4,4,11,11-tetramethyl-3,5,7,10,12-pentaoxatricyclo[7.3.0.02,6]dodecan-6-yl]methylamino]propanoyl]amino]acetyl]amino]acetic acid | 177895-42-0

• 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: 2-[[2-[[(2S)-3-(4-hydroxyphenyl)-2-[[(1R,2S,6S,9R)-4,4,11,11-tetramethyl-3,5,7,10,12-pentaoxatricyclo[7.3.0.02,6]dodecan-6-yl]methylamino]propanoyl]amino]acetyl]amino]acetic acid
• CAS: 177895-42-0
• 化学式: C₂₅H₃₅N₃O₁₀
• 分子量: 537.567
• InChiKey: MWQPRZRISHYKFN-YXGFUMDTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -2.4
• 重原子数：
  38
• 可旋转键数：
  10
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  174
• 氢给体数：
  5
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  2-[[2-[[(2S)-3-(4-hydroxyphenyl)-2-[[(1R,2S,6S,9R)-4,4,11,11-tetramethyl-3,5,7,10,12-pentaoxatricyclo[7.3.0.02,6]dodecan-6-yl]methylamino]propanoyl]amino]acetyl]amino]acetic acid 在 三氟乙酸 作用下， 以 水 为溶剂， 反应 24.0h， 以77%的产率得到N-(1-deoxy-D-fructos-1-yl)-L-tyrosylglycylglycine
  参考文献：
  名称：

  Synthesis and¹³C NMR investigation of novel Amadori compounds (1-amino-1-deoxy-D-fructose derivatives) related to the opioid peptide, leucine–enkephalin

  摘要：

  The N-(1-deoxy-D-fructos-1-yl) derivatives (Amadori compounds) of the endogenous opioid pentapeptide, leucine-enkephalin (11), leucine-enkephalin methyl ester (12) and of structurally related peptides (9, 10) are synthesized. The equilibrium compositions of the prepared Amadori compounds 9-12 in D2O and [H-2(6)]DMSO are determined using C-13 NMR spectroscopy. In water, the beta-pyranose, a-furanose and beta-furanose forms are detected, the beta-pyranose tautomer being the most abundant at equilibrium (67-75%). The alpha-pyranose form and open-chain keto form are not detected. In dimethyl sulfoxide, the equilibrium compositions of 9-12 are markedly shifted towards a higher proportion of furanose forms, amounting to two-thirds of the mixture. In addition to the alpha- and beta-furanoses and beta-pyranose tautomers, DMSO solutions of compounds 9-12 contain at equilibrium a relatively high proportion of the acyclic hydrate (gem-diol) form (ca. 10%).

  DOI：

  10.1039/p29960000789
• 作为产物：
  描述：

  2,3:4,5-bis-O-(isopropylidene)-D-fructopyranose aldehyde 在 sodium cyanoborohydride 、 sodium carbonate 、 N,N'-二环己基碳二亚胺 作用下， 以 甲醇 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 6.0h， 生成 2-[[2-[[(2S)-3-(4-hydroxyphenyl)-2-[[(1R,2S,6S,9R)-4,4,11,11-tetramethyl-3,5,7,10,12-pentaoxatricyclo[7.3.0.02,6]dodecan-6-yl]methylamino]propanoyl]amino]acetyl]amino]acetic acid
  参考文献：
  名称：

  Synthesis and¹³C NMR investigation of novel Amadori compounds (1-amino-1-deoxy-D-fructose derivatives) related to the opioid peptide, leucine–enkephalin

  摘要：

  The N-(1-deoxy-D-fructos-1-yl) derivatives (Amadori compounds) of the endogenous opioid pentapeptide, leucine-enkephalin (11), leucine-enkephalin methyl ester (12) and of structurally related peptides (9, 10) are synthesized. The equilibrium compositions of the prepared Amadori compounds 9-12 in D2O and [H-2(6)]DMSO are determined using C-13 NMR spectroscopy. In water, the beta-pyranose, a-furanose and beta-furanose forms are detected, the beta-pyranose tautomer being the most abundant at equilibrium (67-75%). The alpha-pyranose form and open-chain keto form are not detected. In dimethyl sulfoxide, the equilibrium compositions of 9-12 are markedly shifted towards a higher proportion of furanose forms, amounting to two-thirds of the mixture. In addition to the alpha- and beta-furanoses and beta-pyranose tautomers, DMSO solutions of compounds 9-12 contain at equilibrium a relatively high proportion of the acyclic hydrate (gem-diol) form (ca. 10%).

  DOI：

  10.1039/p29960000789

文献信息

• CD and FTIR spectroscopic studies of Amadori compounds related to the opioid peptides
  作者：Štefica Horvat、Andreja Jakas、Elemér Vass、János Samu、Miklós Hollósi

  DOI：10.1039/a700499k

  日期：——

  Circular dichroism (CD) and Fourier transform infrared (FTIR) spectroscopy have been used to investigate conformational effects of glycation on the secondary structure of opioid peptide Leu-enkephalin and on structurally related peptides in 2,2,2-trifluoroethanol (TFE) solution. CD spectral analysis of Leu-enkephalin-related Amadori compounds revealed that attachment of the protected or free sugar may influence not only the distribution of the backbone but also the side-chain conformation of the Tyr moiety. The amide I region of the FTIR spectra analysed by self-deconvolution and curve-fitting methods revealed that Leu-enkephalin is present as a mixture of β-sheet and γ-turn conformers in TFE solution, while its methyl ester likely adopts a β-turn conformation. FTIR spectroscopy has shown that no major spectral changes occur in the peptide part of glycated (Amadori) compounds as compared to parent peptides. The structurally related Tyr-Gly-Gly tripeptide derivatives contain amide I components at ca. 1630 and ca. 1645 cm-1 consistent with the presence of γ-turns with strong and weak 1 â†� 3 H-bondings, respectively. The attachment of the protected or free sugar moiety to pentapeptides appears to destabilize β-turns but not to affect H-bonded γ-turns. In the spectra of Amadori compounds containing a free sugar moiety, the component band at ca. 1730 cm-1 suggests the presence of the open-chain sugar form. Based on the studies presented herein, FTIR spectroscopy is shown to be a powerful tool for the structural analysis of glycated peptides, in particular for the detection of the keto form of the sugar and turn conformations of the peptide part of the molecule.

  圆二色性 (CD) 和傅里叶变换红外 (FTIR) 光谱学已被用来研究构象效应 阿片肽亮氨酸脑啡肽二级结构的糖化 以及 2,2,2-三氟乙醇 (TFE) 中结构相关的肽 解决方案。亮氨酸脑啡肽相关的 Amadori 的 CD 光谱分析 化合物表明，受保护糖或游离糖的附着可能 不仅影响骨干的分布， Tyr 部分的侧链构象。酰胺 I 区 通过自解卷积和曲线拟合方法分析 FTIR 光谱 表明亮氨酸脑啡肽以混合物形式存在 TFE 中的 β-折叠和 γ-转角构象异构体 溶液，而其甲酯可能采用β-转角 构象。 FTIR 光谱显示没有重大光谱变化 与相比，发生在糖化（Amadori）化合物的肽部分 母肽。结构相关的 Tyr-Gly-Gly 三肽 衍生物含有约 酰胺 I 组分。 1630 和约。 1645 cm-1 与存在一致 强弱 γ 转弯 1 → 3 分别为H键。受保护糖或游离糖的附着 五肽的部分似乎会破坏β-转角的稳定性，但 不影响氢键γ-转角。在阿马多里的光谱中 含有游离糖部分的化合物，其组分带位于约。 1730 cm-1 表明存在开链 糖形式。根据本文提出的研究，FTIR 光谱法 被证明是糖化结构分析的有力工具 肽，特别是用于检测糖的酮形式 并转动分子肽部分的构象。