methyl 3,6-di-O-benzyl-2-O-(2-naphthylmethyl)-1-thio-4-O-triethylsilyl-α-D-mannopyranoside | 1350309-44-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 3,6-di-O-benzyl-2-O-(2-naphthylmethyl)-1-thio-4-O-triethylsilyl-α-D-mannopyranoside
• 英文别名: triethyl-[(2R,3R,4R,5S,6R)-6-methylsulfanyl-5-(naphthalen-2-ylmethoxy)-4-phenylmethoxy-2-(phenylmethoxymethyl)oxan-3-yl]oxysilane
• CAS: 1350309-44-2
• 化学式: C₃₈H₄₈O₅SSi
• 分子量: 644.948
• InChiKey: KROULTRALFKZCN-KGUSBQQXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.01
• 重原子数：
  45
• 可旋转键数：
  16
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  71.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 3,6-di-O-benzyl-2-O-(2-naphthylmethyl)-1-thio-4-O-triethylsilyl-α-D-mannopyranoside 在 2,6-二叔丁基-4-甲基吡啶 、 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 52.0h， 生成 4-methoxyphenyl 3,6-di-O-benzyl-4-O-triethylsilyl-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：

  methyl 4,6-O-benzylidene-1-thio-α-D-mannopyranoside 在 咪唑 、 2,6-二甲基吡啶 、 三乙基硅烷 、 四丁基氟化铵 、 sodium hydride 、 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 158.0h， 生成 methyl 3,6-di-O-benzyl-2-O-(2-naphthylmethyl)-1-thio-4-O-triethylsilyl-α-D-mannopyranoside
  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

• 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.