Pent-4-enyl 4,6-O-benzylidene-α-D-glucopyranoside | 113533-74-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: Pent-4-enyl 4,6-O-benzylidene-α-D-glucopyranoside
• 英文别名: (2R,4aR,6S,7R,8R,8aS)-6-pent-4-enoxy-2-phenyl-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxine-7,8-diol
• CAS: 113533-74-7
• 化学式: C₁₈H₂₄O₆
• 分子量: 336.385
• InChiKey: KZTBMTNXSWESDD-KKFZBWNWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  24
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  77.4
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  Pent-4-enyl 4,6-O-benzylidene-α-D-glucopyranoside 在 palladium on activated charcoal sodium hydroxide 、 9-borabicyclo[3.3.1]nonane dimer 、 sodium azide 、 4 A molecular sieve 、 氢气 、 四丁基硫酸氢铵 、 三乙胺 、 三氟甲烷磺酸甲酯 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 、 水 、 溶剂黄146 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 196.83h， 生成 5'-(1''-pyr-1'''enylbutyramido)pentyl α-D-glucopyranosyl-(1->3)-α-D-glucopyranoside
  参考文献：
  名称：

  荧光标记的葡糖苷酶II的二糖底物的合成。

  摘要：

  荧光标记的二糖Glcalpha（1→3）GlcalphaOR和Glcalpha（1→3）ManalphaOR都是糖蛋白加工酶葡糖苷酶II的两个底物，是通过使用正戊烯基连接子在异头位置。这允许通过一系列的氧化氢硼化，甲磺酰化，叠氮化物置换，伴随整体脱保护的还原和肽偶联而引入a丁酸标记。通过使用三氟甲磺酸甲酯作为促进剂，很容易在正戊烯基糖苷存在下选择性活化全硫代糖苷。

  DOI：

  10.1016/s0008-6215(03)00255-6
• 作为产物：
  描述：

  pent-4-enyl D-glucopyranoside 在 吡啶 、 4-甲基苯磺酸吡啶 、 potassium carbonate 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 3.5h， 生成 Pent-4-enyl 4,6-O-benzylidene-α-D-glucopyranoside
  参考文献：
  名称：

  A Solvation-Assisted Model for Estimating Anomeric Reactivity. Predicted versus Observed Trends in Hydrolysis of n-Pentenyl Glycosides¹

  摘要：

  An attempt has been made to predict qualitative trends in reactivity at the anomeric center, using N-bromosuccinimide-induced hydrolysis of n-pentenyl glycosides (NPGs) as the experimental model. Calculated relative activation energies based on internal energy differences between a reactant and the associated intermediate are not always in agreement with experimental observations. However, solvation energies obtained by the generalized Born surface area model in MacroModel developed by Still et al. give modified activation energies that are in excellent agreement with the experimentally observed trends. It is shown that the solvation model does not disturb the normally observed reactivity trends that can be rationalized on the basis of internal energies alone. The value of the methodology has been demonstrated for several substrates by first-calculating their relative activation energies, then testing them experimentally, and finding excellent agreement with predictions.

  DOI：

  10.1021/jo9601223

文献信息

• n-Pentenyl Glycoside Based Methodology for Determining the Relative Reactivities of Variously Protected Pairs of Glycosides
  作者：Bruce G. Wilson、Bert Fraser-Reid

  DOI：10.1021/jo00107a008

  日期：1995.1

  The relative rate of hydrolysis of an alpha/beta anomeric pair of glycosides is generally considered to provide insight into various factors that influence anomeric reactivity. However the fact that such hydrolyses are usually carried out with aqueous acids severely limits the range of substrates that can studied. This limitation is overcome with n-pentenyl glycosides (NPGs) which are hydrolyzed under neutral, oxidative conditions. A procedure is described in which a pair (e.g. alpha(1)/beta(1), alpha(1)/beta(2), beta(1)/beta(2), etc.) of NPGs is made to compete for an insufficient amount of N-bromosuccinimide, the relative rates of reaction being determined from HPLC peak heights of the unreacted starting materials. Some commonly used acid labile protecting groups, e.g. cyclic acetals and acetyl, are shown to exert profound effects upon relative and absolute rates of anomeric activation.
• Synthesis of fluorescence-labelled disaccharide substrates of glucosidase II
  作者：Ian Cumpstey、Terry D Butters、Richard J Tennant-Eyles、Antony J Fairbanks、Robert R France、Mark R Wormald

  DOI：10.1016/s0008-6215(03)00255-6

  日期：2003.9

  The fluorescence-labelled disaccharides Glcalpha(1-->3)GlcalphaOR and Glcalpha(1-->3)ManalphaOR, both substrates for the glycoprotein-processing enzyme glucosidase II, were synthesised via the use of a n-pentenyl-derived linker at the anomeric position. This allowed incorporation of a pyrenebutyric acid label, via a sequence of oxidative hydroboration, mesylation, azide displacement, reduction with

  荧光标记的二糖Glcalpha（1→3）GlcalphaOR和Glcalpha（1→3）ManalphaOR都是糖蛋白加工酶葡糖苷酶II的两个底物，是通过使用正戊烯基连接子在异头位置。这允许通过一系列的氧化氢硼化，甲磺酰化，叠氮化物置换，伴随整体脱保护的还原和肽偶联而引入a丁酸标记。通过使用三氟甲磺酸甲酯作为促进剂，很容易在正戊烯基糖苷存在下选择性活化全硫代糖苷。
• A Solvation-Assisted Model for Estimating Anomeric Reactivity. Predicted versus Observed Trends in Hydrolysis of <i>n</i>-Pentenyl Glycosides¹
  作者：C. Webster Andrews、Robert Rodebaugh、Bert Fraser-Reid

  DOI：10.1021/jo9601223

  日期：1996.1.1

  An attempt has been made to predict qualitative trends in reactivity at the anomeric center, using N-bromosuccinimide-induced hydrolysis of n-pentenyl glycosides (NPGs) as the experimental model. Calculated relative activation energies based on internal energy differences between a reactant and the associated intermediate are not always in agreement with experimental observations. However, solvation energies obtained by the generalized Born surface area model in MacroModel developed by Still et al. give modified activation energies that are in excellent agreement with the experimentally observed trends. It is shown that the solvation model does not disturb the normally observed reactivity trends that can be rationalized on the basis of internal energies alone. The value of the methodology has been demonstrated for several substrates by first-calculating their relative activation energies, then testing them experimentally, and finding excellent agreement with predictions.