4-methoxyphenyl 2,3-di-O-benzoyl-α-D-xylopyranoside | 1350309-48-6

• 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-di-O-benzoyl-α-D-xylopyranoside
• 英文别名: [(2R,3R,4S,5R)-3-benzoyloxy-5-hydroxy-2-(4-methoxyphenoxy)oxan-4-yl] benzoate
• CAS: 1350309-48-6
• 化学式: C₂₆H₂₄O₈
• 分子量: 464.472
• InChiKey: RRJSOAZPABYFII-ZGXDEKTJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  34
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  101
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  4-methoxyphenyl 2,3-di-O-benzoyl-α-D-xylopyranoside 在 吡啶 、 2,6-二叔丁基-4-甲基吡啶 、 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 二氯甲烷 为溶剂， 反应 25.5h， 生成 4-methoxyphenyl 2-O-acetyl-3,6-di-O-benzyl-4-O-triisopropylsilyl-β-D-mannopyranosyl-(1->4)-2,3-di-O-benzoyl-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 吡啶 、 咪唑 、 4-二甲氨基吡啶 、 三氟甲磺酸三甲基硅酯 、 四丁基氟化铵 、 sodium methylate 、 4-甲基苯磺酸吡啶 、 溶剂黄146 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 167.5h， 生成 4-methoxyphenyl 2,3-di-O-benzoyl-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

• Bimodal Glycosyl Donors Protected by 2-<i>O-</i>(<i>ortho</i>-Tosylamido)benzyl Group
  作者：Feiqing Ding、Akihiro Ishiwata、Yukishige Ito

  DOI：10.1021/acs.orglett.8b01922

  日期：2018.7.20

  A glucosyl donor equipped with C2-o-TsNHbenzyl ether was shown to provide both α- and β-glycosides stereoselectivity, by changing the reaction conditions. Namely, β-glycosides were selectively obtained when the trichloroacetimidate was activated by Tf2NH. On the other hand, activation by TfOH in Et2O provided α-glycosides as major products. This “single donor” approach was employed to assemble naturally

  通过改变反应条件，显示了配备有C 2 -o- TsNH苄基醚的葡糖基供体同时提供α-和β-糖苷的立体选择性。即，当通过Tf 2 NH激活三氯乙酰亚胺酸酯时，选择性地获得β-糖苷。另一方面，通过TfOH在Et 2 O中的活化提供了α-糖苷作为主要产物。这种“单一供体”的方法被用来装配自然三糖α-发生d -Glc-（→2 1）-α- d -Glc-（1→6） - d -Glc和它的端基异构体。
• Synthetic Study and Structural Analysis of the Antifreeze Agent Xylomannan from Upis ceramboides
  作者：Akihiro Ishiwata、Ayaka Sakurai、Yoshiyuki Nishimiya、Sakae Tsuda、Yukishige Ito

  DOI：10.1021/ja208528c

  日期：2011.12.7

  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.