methyl 2,3,4-tri-O-benzyl-6-O-(β-D-glucopyranosyl)-α-D-glucopyranoside | 1012045-70-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,3,4-tri-O-benzyl-6-O-(β-D-glucopyranosyl)-α-D-glucopyranoside
• 英文别名: Glc(b1-6)[Bn(-2)][Bn(-3)][Bn(-4)]a-Glc1Me；(2R,3S,4S,5R,6R)-2-(hydroxymethyl)-6-[[(2R,3R,4S,5R,6S)-6-methoxy-3,4,5-tris(phenylmethoxy)oxan-2-yl]methoxy]oxane-3,4,5-triol
• CAS: 1012045-70-3
• 化学式: C₃₄H₄₂O₁₁
• 分子量: 626.701
• InChiKey: QVTHJILFYWAGCT-DRQYBGAUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  45
• 可旋转键数：
  14
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  146
• 氢给体数：
  4
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  methyl 2,3,4-tri-O-benzyl-6-O-(β-D-glucopyranosyl)-α-D-glucopyranoside 、 碳酸二异丙酯 在 2,4,6-三甲基吡啶 、 (2S,5S)-2,5-bis[[(2S)-3-(1H-indol-3-yl)-1-(octyloxy)-1-oxopropan-2-ylamino]carbonyl]-1-(pyridin-4-yl)pyrrolidine 作用下， 以 氯仿 为溶剂， 反应 12.0h， 生成 methyl 6-O-(4-O-isobutyryl-β-D-glucopyranosyl)-2,3,4-tri-O-benzyl-α-D-glucopyranoside
  参考文献：
  名称：

  Functional Group Tolerance in Organocatalytic Regioselective Acylation of Carbohydrates

  摘要：

  Organocatalytic regioselective acylation of mono- and disaccaharides with various functionalized acid anhydrides has been developed. Acylation Of octyl beta-D-glucopyranoside with acid anhydrides derived from alpha-amino acids, cinnamic acid, and gallic acid took place at C(4)-OH with 67-94% regioselectivity in the presence of catalyst 1. Regioselective acylation of disaccharides with functionalized acid anhydrides was also achieved with 78-94% selectivity. Especially, a disaccharide with seven free hydroxy groups (X = OH, R' = H) underwent acylation at C(4)-OH with 78% regioselectivity in the presence of 1. Thus, functional group tolerance in the regioselective acylation catalyzed by I was found to be high.

  DOI：

  10.1021/jo901569v
• 作为产物：
  描述：

  methyl 2,3,4,6-tetra-O-(4-acetamidophenyl)-β-D-glucopyranosyl-(1→6)-2,3,4-tri-O-benzyl-α-D-glucopyranoside 在 ammonium cerium (IV) nitrate 作用下， 以 水 、 乙腈 为溶剂， 反应 0.08h， 生成 methyl 2,3,4-tri-O-benzyl-6-O-(β-D-glucopyranosyl)-α-D-glucopyranoside
  参考文献：
  名称：

  使用O-芳基保护的糖基供体进行β选择性糖基化

  摘要：

  已开发出包含多个对位取代的O-芳基保护基的新糖基供体，并评估了其对糖基化反应的立体选择性。通过使用受4-硝基苯基（NP）基团保护的硫糖苷，可以实现高度β-选择性糖基化反应，并通过使用相应的三氟甲磺酸二芳基碘铵引入。对几个糖基供体的立体选择性分析表明，β-糖苷是通过从相应的α-糖基三氟甲磺酸酯中以S N 2型取代获得的。可以通过还原硝基和酰化，然后用硝酸铈铵（CAN）氧化来除去NP基团。

  DOI：

  10.1002/asia.201900700

文献信息

• Application of Glycosyl Thioimidates in Solid-Phase Oligosaccharide Synthesis
  作者：M. Cristina Parlato、Medha N. Kamat、Haisheng Wang、Keith J. Stine、Alexei V. Demchenko

  DOI：10.1021/jo701902f

  日期：2008.3.1

  S-benzoxazolyl (SBox) and S-thiazolinyl (STaz) glycosides, were investigated as glycosyl donors for solid-phase oligosaccharide synthesis. It was demonstrated that these derivatives are suitable for both glycosyl acceptor-bound and glycosyl donor-bound strategies, commonly employed in resin-supported oligosaccharide synthesis.

  研究了两类稳定的硫代酰亚胺基衍生物，即S-苯并恶唑基（SBox）和S-噻唑啉基（STaz）糖苷，作为固相寡糖合成的糖基供体。已证明这些衍生物既适用于糖基受体结合的策略，也适用于糖基供体结合的策略，通常用于树脂支持的寡糖合成中。
• Approach Toward Reversal of Chemoselectivity in Catalytic Silylation of Pyranosides
  作者：Hisashi Hashimoto、Yoshihiro Ueda、Koki Fujimura、Kiyosei Takasu、Takeo Kawabata

  DOI：10.1002/ejoc.202200949

  日期：2022.10.7

  C(3)−OH-selective silylation of pyranosides was developed (3 examples, up to 70 % selectivity). While DMAP-catalyzed silylation of 1 gave O-6-silylate A exclusively, ent-C1 enabled to directly afford the secondary C(3)−OH silylate B. This the first example of selective silylation of the secondary OH at C(3) in the presence of the free primary C(6)−OH of pyranosides under the catalyst-controlled conditions

  开发了吡喃糖苷的催化二级 C(3)-OH 选择性甲硅烷基化（3 个例子，高达 70% 的选择性）。虽然 DMAP 催化的1甲硅烷基化仅产生O -6-甲硅烷基化物A，但ent - C1能够直接提供二级 C(3)-OH 甲硅烷基化物B。这是在催化剂控制的条件下，在吡喃糖苷的游离伯 C(6)-OH 存在下，仲 OH 在 C(3) 上选择性甲硅烷基化的第一个例子。