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。
• Functional Group Tolerance in Organocatalytic Regioselective Acylation of Carbohydrates
  作者：Yoshihiro Ueda、Wataru Muramatsu、Kenji Mishiro、Takumi Furuta、Takeo Kawabata

  DOI：10.1021/jo901569v

  日期：2009.11.20

  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.
• β‐Selective Glycosylation by Using <i>O</i> ‐Aryl‐Protected Glycosyl Donors
  作者：Yuji Otsuka、Toshihiro Yamamoto、Koichi Fukase

  DOI：10.1002/asia.201900700

  日期：2019.8

  introduced by using the corresponding diaryliodonium triflate. Analysis of the stereoselectivities of several glycosyl donors indicated that the β‐glycosides were obtained through an SN2‐type displacement from the corresponding α‐glycosyl triflate. The NP group could be removed by reduction of the nitro group and acylation, followed by oxidation with ceric ammonium nitrate (CAN).

  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。