methyl 2,3,4-tri-O-acetyl-β-D-glucopyranosyluronate-(1<*>6)-1,2:3,5-di-O-isopropylidene-α-D-glucofuranose | 157224-12-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子
• 英文名称: methyl 2,3,4-tri-O-acetyl-β-D-glucopyranosyluronate-(1<*>6)-1,2:3,5-di-O-isopropylidene-α-D-glucofuranose
• 英文别名: 6-O-(methyl 2',3',4'-tri-O-acetyl-β-D-glucuronatopyranosyl)-1,2;3,5-di-O-isopropylidene-α-D-glucofuranose
• CAS: 157224-12-9
• 化学式: C₂₅H₃₆O₁₅
• 分子量: 576.552
• InChiKey: VVMLYRLNNHSQBC-COTXGMHWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.09
• 重原子数：
  40.0
• 可旋转键数：
  7.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.84
• 拓扑面积：
  169.81
• 氢给体数：
  0.0
• 氢受体数：
  15.0

反应信息

• 作为反应物：
  描述：

  methyl 2,3,4-tri-O-acetyl-β-D-glucopyranosyluronate-(1<*>6)-1,2:3,5-di-O-isopropylidene-α-D-glucofuranose 在 吡啶 、 2,4,6-三甲基吡啶 、 calcium sulfate 、 Amberlite IR-120 (H+ form) 、 氢溴酸 、 氰化汞 、 溶剂黄146 、 mercury dibromide 、 lithium iodide 作用下， 以 二氯甲烷 、 溶剂黄146 为溶剂， 反应 26.0h， 生成 (2S,3S,4S,5R,6R)-6-[[(2R,3S,4S,5R,6R)-6-[[(3S,4aR,6aR,6bS,8aS,11S,12aR,14aR,14bS)-11-carboxy-4,4,6a,6b,8a,11,14b-heptamethyl-14-oxo-2,3,4a,5,6,7,8,9,10,12,12a,14a-dodecahydro-1H-picen-3-yl]oxy]-3,4,5-trihydroxyoxan-2-yl]methoxy]-3,4,5-trihydroxyoxane-2-carboxylic acid
  参考文献：
  名称：

  Synthesis of glycyrrhetic acid diglycosides and their cytoprotective activities against CCl4--induced hepatic injury in vitro

  摘要：

  Glycyrrhetic acid diglycosides 16, 24, 25, 42 and 46, with respectively beta-D-glucuronopyranosyl-(1-->3)-beta-D-glucopyranose, -(1-->6)-alpha-D-glucopyranose, -(1-->6)-beta-D-glucopyranose, -(1-->6)-beta-D-galactopyranose, and beta-D-galacturonopyranosyl-(-->2)-beta-D-glucopyranose as sugar components at the O-3 positions on the aglycons, were synthesized. In vitro cytoprotective activities, against CCl4-induced hepatic injury, of the synthetic diglycosides, methyl beta-D-glucuronopyranosyl-(1-->4)-alpha-D-glucopyranosyl-D-glycyrrhetinate 33 and methyl esters 15 and 23 (the precursors of 16 and 24 respectively) were compared with those of glycyrrhizin 1 and beta-D-glucuronopyranosyl-(1-->2)-beta-D-glucopyranosyl-glycyrrhetic acid 2. Of the glycosides 16, 24, and 25, with beta-D-glucuronopyranosyl-glucopyranose as the sugar component, 16 and 24 were as cytoprotective as 1 and 2, whereas 25 showed no remarkable activity. From stereomodels of the glycosides these differences in activity were inferred to be due to the stereochemistries of the terminal beta-D-glucuronopyranoses in the molecules. Glycoside 46, in which the terminal beta-D-glucuronopyranose of 2 was replaced by beta-D-galacturonopyranose, was as potent as 2. Further, it was confirmed that a free COOH group on the E ring of aglycon was essential for the activity.

  DOI：

  10.1016/0223-5234(96)89552-3
• 作为产物：
  描述：

  双丙酮葡萄糖 、 乙酰溴-Alpha-D-葡萄糖酮酸甲基酯 在 氰化汞 作用下， 以 硝基甲烷 、 苯 为溶剂， 反应 16.0h， 以2.5%的产率得到methyl 2,3,4-tri-O-acetyl-β-D-glucopyranosyluronate-(1<*>3)-1,2:5,6-di-O-isopropylidene-α-D-glucofuranose
  参考文献：
  名称：

  Virtual 1H-1H spin-spin coupling in a linear five-spin system on the pyranose rings of some glucuronides

  摘要：

  In the H-1 NMR spectra of methyl 2,3,4-tri-O-acetyl-beta D-glucopyranosyluronate-(1 --> 3)- 1,2:5,6-di-O-isopropylidene-alpha-D-glucofuranose (6) and methyl 2,3,4-tri-O-acetyl-beta-D-glucopyranosyluronate-(l --> 6)-1,2:3,5-di-O-isopropylidene-alpha-D-glucofuranose (7), which were obtained by the reaction of 1,2;5,6-di-O-isopropylidene-alpha-D-glucofuranose (1) with methyl 2,3,4-tri-O-acetyl-alpha-D-glucopyranosyluronate bromide (5) in the presence of Hg(CN), in 1:1 benzene-nitromethane at 45 degrees C, protons on both beta-D-glucopyranosyluronate rings were observed as very complex signals that could not be interpreted by first-order analysis. Similar complex signals were also observed for the protons on the beta-D-glucopyranosyluronate rings that were sugar components of some triterpenoidal glycosides (13-15). These complex signals were determined to be due to virtual long-range spin-spin coupling in the linear five-spin system on the glucopyranosyluronate rings of the glucuronides by H-1, C-13, H-C COSY, 1D HOHAHA, and spin-simulation spectroscopies.

  DOI：

  10.1016/0008-6215(94)84075-x