methyl 2,6-di-O-benzyl-3-O-acetyl-α-D-glucopyranoside | 203717-53-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,6-di-O-benzyl-3-O-acetyl-α-D-glucopyranoside
• 英文别名: [(2S,3R,4S,5R,6R)-5-hydroxy-2-methoxy-3-phenylmethoxy-6-(phenylmethoxymethyl)oxan-4-yl] acetate
• CAS: 203717-53-7
• 化学式: C₂₃H₂₈O₇
• 分子量: 416.471
• InChiKey: ZZGXQWHNUUSHMM-ZQGJOIPISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  30
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  83.4
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl 2,6-di-O-benzyl-3-O-acetyl-α-D-glucopyranoside 在 吡啶 、 四氮唑 、 sodium hydroxide 、 sodium azide 作用下， 以 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 36.0h， 生成 methyl 4-deoxy-2,6-di-O-benzyl-3-keto-α-D-galactopyranoside
  参考文献：
  名称：

  A New Reaction for the Direct Conversion of 4-Azido-4-deoxy-d-galactoside into a 4-Deoxy-d-erythro-hexos-3-ulose

  摘要：

  A new one-step reaction has been developed for converting 4-azido-4-deoxy-D-galactoside into 4-deoxy-D-erythro-hexos-3-ulose by phosphoramidites and tetrazole. It is proposed that the new reaction proceeds via an intramolecular Staudinger reaction of the phosphite A intermediate and a tetrazole-catalyzed elimination reaction of the resultant phosphorimidate. Tetrazole appears to be playing a unique role by acting as a bifunctional catalyst to facilitate the elimination reaction.

  DOI：

  10.1021/ol0499046
• 作为产物：
  描述：

  苯甲醛二甲缩醛 在 吡啶 、 盐酸 、 sodium hydroxide 、 sodium tetrahydroborate 、 四丁基碘化铵 作用下， 以 二氯甲烷 、 水 为溶剂， 生成 methyl 2,6-di-O-benzyl-3-O-acetyl-α-D-glucopyranoside
  参考文献：
  名称：

  A New Reaction for the Direct Conversion of 4-Azido-4-deoxy-d-galactoside into a 4-Deoxy-d-erythro-hexos-3-ulose

  摘要：

  A new one-step reaction has been developed for converting 4-azido-4-deoxy-D-galactoside into 4-deoxy-D-erythro-hexos-3-ulose by phosphoramidites and tetrazole. It is proposed that the new reaction proceeds via an intramolecular Staudinger reaction of the phosphite A intermediate and a tetrazole-catalyzed elimination reaction of the resultant phosphorimidate. Tetrazole appears to be playing a unique role by acting as a bifunctional catalyst to facilitate the elimination reaction.

  DOI：

  10.1021/ol0499046

文献信息

• Monoacetylation of Carbohydrate Diols via Transesterification with Ethyl Acetate
  作者：Xuyu Liu、Bernd Becker、Matthew A. Cooper

  DOI：10.1071/ch12518

  日期：——

  Monoacetylation of secondary diols in protected monosaccharides was achieved with ethyl acetate as acyl donor and sodium tert-butoxide as a base. The regioseletivity of the reaction varied depending on the substrate. This new method provides a simple, fast, and efficient method to access selectively acetylated carbohydrates that is compatible with acid-sensitive protecting groups.

  以乙酸乙酯为酰基供体，以叔丁醇钠为碱，在保护的单糖中使仲二醇单乙酰化。反应的区域选择性取决于底物。这种新方法提供了一种简单，快速，有效的方法来访问与酸敏感的保护基团兼容的选择性乙酰化碳水化合物。
• Synthesis, NMR spectroscopy and conformational studies of the four anomeric methyl glycosides of the trisaccharide D-Glcp-(1→3)-[D-Glcp-(1→4)]-α-D-Glcp
  作者：Peter Söderman、Per-Erik Jansson、Göran Widmalm

  DOI：10.1039/a707346a

  日期：——

  The four anomeric methyl glycosides of the vicinally disubstituted trisaccharide D-Glcp-(1→3)-[D-Glcp-(1→4)]-α-D-Glcp have been synthesized using silver trifluoromethanesulfonate mediated glycosylations. The 1H and 13C NMR resonances have been assigned and used for extraction of glycosylation shifts, i.e. the differences between chemical shifts for signals from the trisaccharides and those of the respective monomers, as well as those derived by addition of the glycosylation shifts for each disaccharide element. Glycosylation shifts are up to 0.5 ppm for proton and 10 ppm for carbon. Deviations from additivity are –0.2–0.1 ppm for proton and –4.5–2.3 ppm for carbon, usually confined to the atoms at the linkage positions. The conformational space spanned for the trisaccharides, and the constituent disaccharides, has been investigated by Metropolis Monte Carlo simulations using the HSEA force field. The α-linked glucosyl groups show larger conformational changes with multiple energy minima, whereas the β-linked glucosyl groups have a single energy minimum, close to that identified for the constituent disaccharide.

  四种脱氧间位二取代的三糖D-Glcp-(1→3)-[D-Glcp-(1→4)]-α-D-Glcp的异构体甲基糖苷已通过三氟甲磺酸银催化的糖苷化反应合成。已对其1H和13C NMR谱峰进行了赋值，并用于提取糖苷化位移，即三糖信号与各自单体信号的化学位移之间的差异，以及对每个二糖单元的糖苷化位移的累加。糖苷化位移的变化范围为质子最多可达0.5 ppm，碳可达10 ppm。偏离加性规律的值则为-0.2至-0.1 ppm（质子）和-4.5至-2.3 ppm（碳），通常集中在连接位置的原子上。通过使用HSEA力场的Metropolis Monte Carlo模拟，研究了三糖及其组成的二糖所涵盖的构象空间。α-链接的葡萄糖基显示出较大的构象变化和多个能量最小点，而β-链接的葡萄糖基则只有一个能量最小点，接近于其组成的二糖所识别的能量最低点。
• Regioselective Reductive Ring Opening of Benzylidene Acetals Using Triethylsilane and Iodine
  作者：Anup Misra、Rajib Panchadhayee

  DOI：10.1055/s-0029-1219798

  日期：2010.5

  Novel reaction conditions have been developed for the regioselective reductive ring opening of benzylidene acetals in carbohydrate derivatives using triethylsilane and molecular iodine. The reaction is fast, compatible with most of the functional groups encountered in the oligosaccharide synthesis, and yields were excellent. The reaction conditions are equally effective in thioglycosides.

  已经开发了新的反应条件，用于使用三乙基硅烷和分子碘对碳水化合物衍生物中的亚苄基缩醛进行区域选择性还原开环。反应速度快，与寡糖合成中遇到的大多数官能团相容，产率极好。反应条件在硫糖苷中同样有效。