methyl 2,3,4-tri-O-benzoyl-6-O-(2,3,4,6-tetra-O-benzyl-β-D-galactopyranosyl)-α-D-glucopyranoside | 194471-78-8

• 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-benzoyl-6-O-(2,3,4,6-tetra-O-benzyl-β-D-galactopyranosyl)-α-D-glucopyranoside
• 英文别名: methyl 2,3,4-tri-O-benzoyl-6-O-(2,3,4,6-tetra-O-benzyl-D-galactopyranosyl)-α-D-glucopyranoside；Bn(-2)[Bn(-3)][Bn(-4)][Bn(-6)]Gal(b1-6)[Bz(-2)][Bz(-3)][Bz(-4)]a-Glc1Me；[(2R,3R,4S,5R,6S)-4,5-dibenzoyloxy-6-methoxy-2-[[(2R,3R,4S,5S,6R)-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-yl]oxymethyl]oxan-3-yl] benzoate
• CAS: 194471-78-8
• 化学式: C₆₂H₆₀O₁₄
• 分子量: 1029.15
• InChiKey: RGZPHINDFHDVMO-OBCQBQLDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.1
• 重原子数：
  76
• 可旋转键数：
  26
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  153
• 氢给体数：
  0
• 氢受体数：
  14

反应信息

• 作为产物：
  描述：

  D-吡喃葡萄糖 在 吡啶 、 4-二甲氨基吡啶 、 1-(苯基亚硫酰基)哌啶 、 2,4,6-三叔丁基吡啶 、 三氟化硼乙醚 、 sodium methylate 、 sodium hydride 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 4.5h， 生成 methyl 2,3,4-tri-O-benzoyl-6-O-(2,3,4,6-tetra-O-benzyl-β-D-galactopyranosyl)-α-D-glucopyranoside
  参考文献：
  名称：

  Directing effect by remote electron-withdrawing protecting groups at O-3 or O-4 position of donors in glucosylations and galactosylations

  摘要：

  Glucosylations and galactosylations of various acceptors with donors possessing an electronwithdrawing benzylsulfonyl, benzoyl, or acetyl group at the O-3 or O-4 position were performed. A beta-directing effect by the benzylsulfonyl group at O-3 of the glucosyl donors and by the benzylsulfonyl and acyl groups at O-4 of the glucosyl donors was observed. In contrast, acyl groups at O-3 of the glucosyl donors and acyl groups at O-3 and O-4 of the galactosyl donors exhibited an alpha-directing effect. The alpha-directing effect is partly considered to remote participation of the acyl groups, whereas the beta-directing effect is somewhat attributed to the S(N)2-like reaction of the acceptor with the glycosyl triflate or the contact ion pair, which is stabilized by remote electron-withdrawing groups. Further evidence for the stability of the alpha-glycosyl triflates was determined by a low-temperature NMR study. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2015.06.014

文献信息

• Iron(<scp>iii</scp>) chloride modulated selective 1,2-trans glycosylation based on glycosyl trichloroacetimidate donors and its application in orthogonal glycosylation
  作者：Mana Mohan Mukherjee、Nabamita Basu、Rina Ghosh

  DOI：10.1039/c6ra21859h

  日期：——

  FeCl3 can also modulate the 1,2-trans selectivity of the reaction of 2-O-alkylated gluco- and galacto-pyranosyl trichloroacetimidates with phenolic compounds leading to the generation of the corresponding β-O-aryl glycosides in excellent yield and selectivity. Apart from these the present methodology has been successfully utilized for double glycosylation and orthogonal glycosylation reactions along

  人们已经集中研究了一种新的糖基化方法，该方法可从10摩尔％的FeCl 3介导的相应的三氯乙酰亚氨酸酯供体有效立体选择性合成β-葡萄糖和半乳糖苷。FeCl 3也已应用于许多基于葡萄糖，半乳糖，甘露糖和鼠李糖的三氯乙酰亚氨酸酯供体，这些供体在C-2位置掺入了各种保护基，从而制备了多种具有优异的1,2-反式选择性的二糖和三糖。FeCl 3还可调节2- O反应的1,2-反式选择性-烷基化的葡糖基和半乳糖基-吡喃糖基三氯乙酰亚胺酸酯与酚类化合物的结合，可导致以优异的产率和选择性生成相应的β- O-芳基糖苷。除此之外，本方法已成功地用于双糖基化和正交糖基化反应，以及在三锅合成的一锅三组分正交糖基化反应中的应用。
• Substoichiometric FeCl3 Activation of Propargyl Glycosides for the Synthesis of Disaccharides and Glycoconjugates
  作者：Jianbo Zhang、Guosheng Sun、Yue Wu、Anqi Liu、Saifeng Qiu、Wan Zhang、Zhongfu Wang

  DOI：10.1055/s-0036-1591525

  日期：2018.3

  Glycosides as glycosyl donors using FeCl3 have been described. Under optimal reaction conditions, three kinds of propargyl glycosides were found to react with steroids and sugar-derived glycosyl acceptors to afford the corresponding disaccharides and glycoconjugates in good to excellent yields (66–91%). Meanwhile, the method can also realize one-pot synthesis of disaccharides, making it an effective

  已经描述了使用 FeCl3 作为糖基供体的糖苷。在最佳反应条件下，发现三种炔丙基糖苷与类固醇和糖衍生的糖基受体反应，以良好至极好的收率（66-91%）提供相应的二糖和糖缀合物。同时，该方法还可实现双糖的一锅法合成，是一种高效、经济、绿色的糖基化方法。
• OFox imidates as versatile glycosyl donors for chemical glycosylation
  作者：Swati S. Nigudkar、Tinghua Wang、Salvatore G. Pistorio、Jagodige P. Yasomanee、Keith J. Stine、Alexei V. Demchenko

  DOI：10.1039/c6ob02230h

  日期：——

  mediated glycosylations wherein 3,3-difluoro-3H-indol-2-yl (OFox) imidates were found to be key intermediates. Both the in situ synthesis from the corresponding glycosyl bromides and activation of the OFox imidates could be conducted in a regenerative fashion. Herein, we extend this study with the main focus on the synthesis of various OFox imidates and their investigation as glycosyl donors for chemical

  以前，我们交流了3,3-二氟己二酮（HOFox）介导的糖基化作用，其中发现3,3-二氟-3 H-吲哚-2-基（OFox）酰亚胺化是关键中间体。无论是在原位由相应的糖基溴化物和亚胺酸酯OFox活化合成可以在再生的方式进行。在这里，我们扩展了这项研究，主要侧重于各种OFox酰亚胺的合成及其作为化学1,2-顺式和1,2-反式糖基化的糖基供体的研究。
• Methyl glycosides are identified as glycosyl donors for the synthesis of glycosides, disaccharides and oligosaccharides
  作者：Srinivasa Rao Vidadala、Srinivas Hotha

  DOI：10.1039/b822526e

  日期：——

  Stable methyl glycosides are identified as glycosyl donors in the presence of AuBr(3) in acetonitrile; a panel of aglycones comprising aliphatic, alicyclic, steroidal and sugar alcohols are examined successfully for the glycosylation reaction and methyl glycosides of di- and tri- saccharides are converted to corresponding tri- and tetra-saccharides exploiting salient features of our novel activation

  在乙腈中存在AuBr（3）的情况下，稳定的甲基糖苷被鉴定为糖基供体；利用我们新颖的激活方案的显着特征，成功地检测了一组包含脂肪族，脂环族，甾族和糖醇的糖苷配基的糖基化反应，并将二糖和三糖的甲基糖苷转化为相应的三糖和四糖。
• Bismuth(V)-Mediated Thioglycoside Activation
  作者：Manibarsha Goswami、Arkady Ellern、Nicola L. B. Pohl

  DOI：10.1002/anie.201304099

  日期：2013.8.5

  A straightforward method utilizing a bismuth(V) compound was developed for the activation of thiopropylglycosides for coupling to various acceptors; good to excellent yields were obtained without applying additional additives/co‐promoters. The method does not require low temperatures, is applicable to a wide variety of carbohydrates, and tolerates different functional groups including alkenes.

  开发了一种简单的利用铋（V）化合物的方法来激活硫丙基丙基糖苷以偶联到各种受体上。在不使用其他添加剂/助促进剂的情况下获得了良好至极好的收率。该方法不需要低温，适用于多种碳水化合物，并且可以耐受包括烯烃在内的不同官能团。