4-methoxyphenyl 2,3-O-isopropylidene-α-D-xylopyranoside | 1350309-59-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-methoxyphenyl 2,3-O-isopropylidene-α-D-xylopyranoside
• CAS: 1350309-59-9
• 化学式: C₁₅H₂₀O₆
• 分子量: 296.32
• InChiKey: YDYCZSVZPLBZKC-XJFOESAGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.31
• 重原子数：
  21.0
• 可旋转键数：
  3.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  66.38
• 氢给体数：
  1.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  4-methoxyphenyl 2,3-O-isopropylidene-α-D-xylopyranoside 在 吡啶 、 咪唑 、 4-二甲氨基吡啶 、 2,6-二叔丁基-4-甲基吡啶 、 四丁基氟化铵 、 sodium methylate 、 4-甲基苯磺酸吡啶 、 sodium hydride 、 溶剂黄146 、 三氟乙酸 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 三氟甲烷磺酸甲酯 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 异丙醇 为溶剂， 反应 144.0h， 生成 4-methoxyphenyl 2,3,6-tri-O-benzyl-β-D-mannopyranosyl-(1->4)-2,3-di-O-benzyl-α-D-xylopyranoside
  参考文献：
  名称：

  Synthetic Study and Structural Analysis of the Antifreeze Agent Xylomannan from Upis ceramboides

  摘要：

  The novel antifreeze factor, xylomannan, first isolated from the freeze-tolerant Alaskan beetle Upis ceramboides, demonstrates a high degree of thermal hysteresis, comparable to that of the most active insect antifreeze proteins. Although the presence of a lipid component in this factor has not yet been verified, it has been proposed that the glycan backbone consists of a beta-D-mannopyranosyl-(1 -> 4)-beta-D-xylopyranose-disaccharide-repeating structure according to MS and NMR analyses. In this contribution, we report the stereoselective synthesis of the tetrasaccharide beta-D-mannopyranosyl-(1 -> 4)-beta-D-xylopyranosyl-(1 -> 4)-beta-D-mannopyranosyl-(1 -> 4)-D-xylopyranoside, a structural component of xylomannan. Our synthesis features the use of 2-naphthylmethyl (NAP)-ether-mediated intramolecular aglycon delivery (IAD) as the key reaction in obtaining beta-mannopyranoside stereoselectively. Various donors for NAP-IAD were tested to determine the most suitable for the purposes of this synthesis. Fragment coupling between a disaccharyl fluoride and a disaccharide acceptor obtained from a common beta-D-mannopyranosyl-(1 -> 4)-beta-D-xylopyranoside derivative was successfully carried out to afford the desired tetrasaccharide in the presence of Cp2HfCl2-AgClO4. Structural analysis of the resulting synthetic tetrasaccharide using NMR techniques and molecular modeling was performed in order to demonstrate the presence of the proposed xylomannan linkages in this molecule.

  DOI：

  10.1021/ja208528c
• 作为产物：
  描述：

  1,2,3,4-四-O-乙酰基吡喃戊糖 在 三氟甲磺酸三甲基硅酯 、 sodium methylate 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 58.0h， 生成 4-methoxyphenyl 2,3-O-isopropylidene-α-D-xylopyranoside
  参考文献：
  名称：

  Synthetic Study and Structural Analysis of the Antifreeze Agent Xylomannan from Upis ceramboides

  摘要：

  The novel antifreeze factor, xylomannan, first isolated from the freeze-tolerant Alaskan beetle Upis ceramboides, demonstrates a high degree of thermal hysteresis, comparable to that of the most active insect antifreeze proteins. Although the presence of a lipid component in this factor has not yet been verified, it has been proposed that the glycan backbone consists of a beta-D-mannopyranosyl-(1 -> 4)-beta-D-xylopyranose-disaccharide-repeating structure according to MS and NMR analyses. In this contribution, we report the stereoselective synthesis of the tetrasaccharide beta-D-mannopyranosyl-(1 -> 4)-beta-D-xylopyranosyl-(1 -> 4)-beta-D-mannopyranosyl-(1 -> 4)-D-xylopyranoside, a structural component of xylomannan. Our synthesis features the use of 2-naphthylmethyl (NAP)-ether-mediated intramolecular aglycon delivery (IAD) as the key reaction in obtaining beta-mannopyranoside stereoselectively. Various donors for NAP-IAD were tested to determine the most suitable for the purposes of this synthesis. Fragment coupling between a disaccharyl fluoride and a disaccharide acceptor obtained from a common beta-D-mannopyranosyl-(1 -> 4)-beta-D-xylopyranoside derivative was successfully carried out to afford the desired tetrasaccharide in the presence of Cp2HfCl2-AgClO4. Structural analysis of the resulting synthetic tetrasaccharide using NMR techniques and molecular modeling was performed in order to demonstrate the presence of the proposed xylomannan linkages in this molecule.

  DOI：

  10.1021/ja208528c

文献信息

• A Stereoselective Glycosylation Approach to the Construction of 1,2‐ <i>trans</i> ‐β‐ <scp>d</scp> ‐Glycosidic Linkages and Convergent Synthesis of Saponins
  作者：Fuzhu Yang、Wu Hou、Dapeng Zhu、Yu Tang、Biao Yu

  DOI：10.1002/chem.202104002

  日期：2022.2

  Direct action: A highly stereoselective glycosylation protocol for the synthesis of 1,2-trans-β-d- or α-l-glycosidic linkages is disclosed, which employs a combination of glycosyl N-phenyltrifluroacetimidates as donors, FeCl3 as promoter, and CH2Cl2/nitrile as solvent and exploits glycosidation via glycosyl α-nitrilium intermediates. A variety of natural saponins containing (1→2)-linked glycan motifs

  直接作用：公开了一种用于合成 1,2-反式-β- d-或 α -l-糖苷键的高度立体选择性糖基化方案，该方案采用糖基N-苯基三氟乙酰亚胺酯作为供体、FeCl 3作为促进剂和CH 2 Cl 2 /腈作为溶剂，通过糖基 α-腈中间体进行糖苷化。因此，通过与 (1→2)-连接的聚糖供体直接糖基化，以收敛的方式合成了多种含有 (1→2)-连接的聚糖基序的天然皂苷。