methyl 2,3,6-tri-O-benzyl-4-O-(2',3',4',6'-tetra-O-benzyl-β-D-mannopyranosyl)-α-D-glucopyranoside | 117894-99-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,3,6-tri-O-benzyl-4-O-(2',3',4',6'-tetra-O-benzyl-β-D-mannopyranosyl)-α-D-glucopyranoside
• 英文别名: methyl (2,3,4,6-tetra-O-benzyl-α-D-mannopyranosyl)-(1→4)-2,3,6-tri-O-benzyl-α-D-glucopyranoside；Bn(-2)[Bn(-3)][Bn(-4)][Bn(-6)]Man(b1-4)[Bn(-2)][Bn(-3)][Bn(-6)]a-Glc1Me；(2S,3R,4S,5R,6R)-2-methoxy-3,4-bis(phenylmethoxy)-6-(phenylmethoxymethyl)-5-[(2S,3S,4S,5R,6R)-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-yl]oxyoxane
• CAS: 117894-99-2
• 化学式: C₆₂H₆₆O₁₁
• 分子量: 987.199
• InChiKey: XGUQGDPCAPRZDC-VRHJCYKTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.5
• 重原子数：
  73
• 可旋转键数：
  26
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  102
• 氢给体数：
  0
• 氢受体数：
  11

反应信息

• 作为产物：
  描述：

  phenyl 2,3,4,6-tetra-O-benzyl-1-thio-α-D-mannopyranoside 在 碳酸氢钠 、 间氯过氧苯甲酸 、 scandium tris(trifluoromethanesulfonate) 、 2,4,6-三叔丁基嘧啶 作用下， 以 二氯甲烷 为溶剂， 反应 2.5h， 生成 methyl 2,3,6-tri-O-benzyl-4-O-(2',3',4',6'-tetra-O-benzyl-β-D-mannopyranosyl)-α-D-glucopyranoside
  参考文献：
  名称：

  立体控制合成糖苷通过用糖基钪砜供体的激活（III），三氟甲磺酸†

  摘要：

  使用三氟甲磺酸scan （III）已经实现了芳基糖基砜供体的活化，并导致了由糖基化后的异构化反应产生的α-甘露糖苷的选择性制备。

  DOI：

  10.1039/c7ob02792c

文献信息

• Blue Light Photocatalytic Glycosylation without Electrophilic Additives
  作者：Peng Wen、David Crich

  DOI：10.1021/acs.orglett.7b00932

  日期：2017.5.5

  employing stable and readily accessible O-glycosyl derivatives of 2,2,6,6-tetramethylpiperidin-1-ol is presented that employs an iridium-based photocatalyst and blue LEDs. The reaction proceeds at room temperature and in the absence of additives other than 4 Å molecular sieves. Stereoselectivities are modest but nevertheless dependent on the anomeric configuration of the donor, suggesting a substantial

  提出了使用2,2,6,6-四甲基哌啶-1-醇的稳定且易于获得的O-糖基衍生物进行糖苷键的光催化形成，该衍生物使用基于铱的光催化剂和蓝色LED。该反应在室温下且在没有4Å分子筛以外的添加剂的情况下进行。立体选择性是适度的，但是取决于供体的异头构型，这表明相当大程度的一致特征。
• Automated Quantification of Hydroxyl Reactivities: Prediction of Glycosylation Reactions
  作者：Chun‐Wei Chang、Mei‐Huei Lin、Chieh‐Kai Chan、Kuan‐Yu Su、Chia‐Hui Wu、Wei‐Chih Lo、Sarah Lam、Yu‐Ting Cheng、Pin‐Hsuan Liao、Chi‐Huey Wong、Cheng‐Chung Wang

  DOI：10.1002/anie.202013909

  日期：2021.5.25

  (Aka) to quantify the nucleophilicity of hydroxyl groups in glycosylation influenced by the steric, electronic and structural effects, providing a connection between experiments and computer algorithms. The subtle reactivity differences among the hydroxyl groups on various carbohydrate molecules can be defined by Aka, which is easily accessible by a simple and convenient automation system to assure

  糖基化反应的立体选择性和产率至关重要，但不可预测。我们已经开发了一个亲核亲核常数（Aka）数据库，用于量化受空间，电子和结构效应影响的糖基化中羟基的亲核性，从而在实验和计算机算法之间建立联系。各种碳水化合物分子上的羟基之间的细微反应性差异可以由Aka定义，Aka可以通过简单便捷的自动化系统轻松访问，以确保高重现性和准确性。通过设计的软件程序“ GlycoComputer”可以组织和处理各种具有明确反应性和启动子的糖基化供体和受体，从而无需复杂的计算过程即可预测糖基化反应。通过随机森林算法进一步验证了Aka的重要性，并通过合成Lewis A骨架测试了适用性，表明可以准确估计立体选择性和产率。
• 6-Nitro-2-benzothiazolyl α-Glucoside and α-Mannoside in β-Selective Glycosylations
  作者：Takashi Hashihayata、Hiroki Mandai、Teruaki Mukaiyama

  DOI：10.1246/bcsj.77.169

  日期：2004.1

  Highly β-selective glucosylations of glycosyl acceptors having a primary hydroxy group with a 6-nitro-2-benzothiazolyl α-glucoside donor 3α proceeded smoothly in the presence of a catalytic amount of trifluoromethanesulfonic acid (TfOH) in CH2Cl2 at −78 °C to afford the corresponding glycosides in high yields. With the use of 3α, β-saccharides could be obtained more dominantly than other α-glucosyl donors such as thioform- and trichloroacet-imidates or fluoride in the glucosylation under the same conditions. Similarly, highly β-selective mannosylations of glycosyl acceptors with a 6-nitro-2-benzothiazolyl α-mannoside donor 18α were carried out smoothly in the presence of a catalytic amount of tetrakis(pentafluorophenyl)boric acid H[B(C6F5)4] to afford the corresponding disaccharides in good to high yields; 18α apparently behaved as a potent donor here for the construction of β-mannoside linkage. Interestingly, in situ anomerization from 18β to 18α was observed when β-mannosyl donor 18β was treated with a catalytic amount of H[B(C6F5)4] in CH2Cl2.

  高度β选择性的糖苷化反应使用6-硝基-2-苯并噻唑基α-葡萄糖苷供体3α，在−78 °C下，添加催化量的三氟甲烷磺酸（TfOH）于CH2Cl2中顺利进行，使得具有一级羟基的糖苷受体生成相应的糖苷，并获得高产率。在相同条件下使用3α时，β-糖苷的生成明显优于其他α-葡萄糖苷供体，如硫甲酸酯、三氯醋酰亚胺或氟化物。同样地，使用6-硝基-2-苯并噻唑基α-甘露糖苷供体18α进行的甘露糖苷化反应在催化量的四氟苯基硼酸H[B(C6F5)4]存在下顺利进行，获得相应的二糖，产率良好至高；18α在这里明显表现为有效的供体，用于构建β-甘露糖苷键。有趣的是，当β-甘露糖苷供体18β与催化量的H[B( )4]在 中反应时，观察到18β向18α的原位异构化。
• Stereoselective β-mannosylations and β-rhamnosylations from glycosyl hemiacetals mediated by lithium iodide
  作者：Imlirenla Pongener、Dionissia A. Pepe、Joseph J. Ruddy、Eoghan M. McGarrigle

  DOI：10.1039/d1sc01300a

  日期：——

  Stereoselective β-mannosylation is one of the most challenging problems in the synthesis of oligosaccharides. Herein, a highly selective synthesis of β-mannosides and β-rhamnosides from glycosyl hemi-acetals is reported, following a one-pot chlorination, iodination, glycosylation sequence employing cheap oxalyl chloride, phosphine oxide and LiI. The present protocol works excellently with a wide range

  立体选择性β-甘露糖基化是寡糖合成中最具挑战性的问题之一。在此，报道了使用廉价的草酰氯、氧化膦和 LiI 进行一锅氯化、碘化、糖基化序列后，从糖基半缩醛中高度选择性地合成 β-甘露糖苷和 β-鼠李糖苷。本协议适用于广泛的糖基受体和武装糖基供体。该方法不需要构象限制的供体或导向基团；建议观察到的高β-选择性是通过碘化锂促进的 α-糖基碘化物的 S N 2 型反应实现的。
• Glycosyl 2-Pyridinecarboxylate as an Effective Glycosyl Donor: Glycosidation of Mannose, 2-Azidosugar, and 2-Deoxysugar into Disaccharides.
  作者：Hironori FURUKAWA、Kazunori KOIDE、Ken-ichi TAKAO、Susumu KOBAYASHI

  DOI：10.1248/cpb.46.1244

  日期：——

  Glycosylation reactions using a glycosyl 2-pyridinecarboxylate as a glycosyl donor were performed. Glycosyl 2-pyridinecarboxylate was designed based on a variation of the Remote Activation Concept and is activated through bidentate coordination to mild Lewis acids such as copper triflate and tin triflate. This method was effective for the glycosidation of not only glucose, but several other sugars such as the mannose-type, 2-azidosugar-type, and 2-deoxysugar-type. Various disaccharides were obtained in excellent yield by this reaction.

  使用 2-吡啶甲酸糖基作为糖基供体进行了糖基化反应。2 吡啶甲酸糖基酯是根据远程活化概念的一种变体设计的，通过与温和的路易斯酸（如三酸铜和三酸锡）的双叉配位而活化。这种方法不仅对葡萄糖的糖苷化有效，而且对甘露糖型、2-叠氮糖型和 2-脱氧糖型等其他几种糖的糖苷化也有效。通过该反应还能以极高的产率获得各种二糖。