methyl 2,3,6-tri-O-benzyl-4-O-(3,4,6-tri-O-benzyl-2-azido-2-deoxy-β-D-glucopyranosyl)-α-D-glucopyranoside

• 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-(3,4,6-tri-O-benzyl-2-azido-2-deoxy-β-D-glucopyranosyl)-α-D-glucopyranoside
• 英文别名: methyl-4-(2-azido-3,4,6-tri-O-benzyl-2-deoxy-β-D-glucopyranosyl)-2,3,6-tri-O-benzyl-α-D-glucopyranoside；methyl 4-O-(2-azido-3,4,6-tri-O-benzyl-2-deoxy-β-D-glucopyranosyl)-2,3,6-tri-O-benzyl-α-D-glucopyranoside；methyl 3,4,6-tri-O-benzyl-2-deoxy-2-azido-β-D-glucopyranosyl-(1→4)-2,3,4-tri-O-benzyl-α-D-glucopyranoside；methyl 2-azido-3,4,6-tri-O-benzyl-2-deoxy-β-D-glucopyranosyl-(1→4)-2,3,6-tri-O-benzyl-α-D-glucopyranoside；methyl 2-azido-3,4,5-tri-O-benzyl-2-deoxy-D-glucopyranosyl-β-(1->4)-2,3,6-tri-O-benzyl-α-D-glucopyranoside；methyl 2,3,6-tri-O-benzyl-4-O-(2-azido-2-deoxy-3,4,6-tri-O-benzyl-β-D-glucopyranosyl)-α-D-glucopyranoside；methyl 2-azido-3,4,6-tri-O-benzyl-2-deoxy-β-D-glucopyranosyl-(1 4)-2,3,6-tri-O-benzyl-α-D-glucopyranoside；methyl 4-O-(2-azido-3,4,6-tri-O-benzyl-2-deoxy-D-gluco-pyranosyl)-2,3,6-tri-O-benzyl-α-D-glucopyranoside；methyl 2,3,6-tri-O-benzyl-4-O-(2-azido-2-deoxy-3,4,6-tri-O-benzyl-D-glucopyranosyl)-α-Dglucopyranoside；(2S,3R,4R,5S,6R)-3-azido-2-[(2R,3R,4S,5R,6S)-6-methoxy-4,5-bis(phenylmethoxy)-2-(phenylmethoxymethyl)oxan-3-yl]oxy-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxane
• 化学式: C₅₅H₅₉N₃O₁₀
• 分子量: 922.088
• InChiKey: KRQLLPIXGZSNNA-UEXVVFBYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9
• 重原子数：
  68
• 可旋转键数：
  24
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  107
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为产物：
  描述：

  2-叠氮基-2-脱氧-D-吡喃葡萄糖1,3,4,6-四乙酸酯 在 甲醇 、 N-碘代丁二酰亚胺 、 三氟甲磺酸三甲基硅酯 、 三氟化硼乙醚 、 sodium 、 sodium hydride 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 、 乙腈 、 丙腈 为溶剂， 反应 23.0h， 生成 methyl 2,3,6-tri-O-benzyl-4-O-(3,4,6-tri-O-benzyl-2-azido-2-deoxy-β-D-glucopyranosyl)-α-D-glucopyranoside
  参考文献：
  名称：

  2-叠氮基-2-脱氧硫糖苷在β-糖苷形成和寡糖合成中的应用

  摘要：

  大多数天然 2-乙酰氨基-2-脱氧糖苷以 1,2-反式-β-糖苷构型存在。本研究调查了 2-叠氮基-2-脱氧硫糖苷在低浓度糖基化条件下用于 1,2-反式-β-糖苷键形成的用途。2-叠氮基-2-脱氧硫糖基底物在一锅寡糖合成中的进一步应用在受保护的β-(16)-N-乙酰氨基葡萄糖三聚体、核心6-丝氨酸偶联物和F1-α丝氨酸偶联物的合成中得到了证明。

  DOI：

  10.1002/ejoc.201200173

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。
• Tuning Reactivity of Glycosyl Imidinium Intermediate for 2-Azido-2-deoxyglycosyl Donors in α-Glycosidic Bond Formation
  作者：Arun B. Ingle、Chin-Sheng Chao、Wei-Cheng Hung、Kwok-Kong Tony Mong

  DOI：10.1021/ol402519c

  日期：2013.10.18

  The chemical properties of nucleophile additives were investigated in a modulated glycosylation context. N-Formylmorpholine (NFM) was found to be an effective modulator for glycosylation with less reactive 2-azido-2-deoxythioglucosyl and thiogalactosyl donors.

  亲核添加剂的化学性质在调制的糖基化环境下进行了研究。发现N-甲酰基吗啉（NFM）是具有较低反应性的2-叠氮基-2-脱氧硫代葡糖基和硫代半乳糖基供体的糖基化的有效调节剂。
• 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。
• Vinyl Glycosides in Oligosaccharide Synthesis (Part 6): 3-Buten-2-YL 2-Azido-2-Deoxy Glycosides and 3-Buten-2-YL 2-Phthalimido-2-Deoxy Glycosides as Novel Glycosyl Donors
  作者：Yu Bai、Geert-Jan Boons、Andrew Burton、Matthew Johnson、Michael Haller

  DOI：10.1080/07328300008544127

  日期：2000.1

  and 19 can be conveniently isomerised by treatment with a catalytic amount of (Ph3P)3RhCl/BuLi to give the active vinyl glycosides 6, 17 and 20 in high yield. These glycosyl donors were successfully used in glycosylations with acceptors 7, 9 and 11. In the case of glycosyl donor 6, the disaccharides 8, 10 and 12 could be obtained as anomeric mixtures or with high α-or β-selectivities depending on the

  据报道潜在活性糖基化策略的扩展，其中3-丁烯-2-基2-脱氧-2-叠氮基糖苷和3-丁烯-2-基2-脱氧-2-邻苯二甲酰亚胺基糖苷被用作制备甲壳素的结构单元。含氨基糖的寡糖。潜基板的烯丙基部分5,16和19可以通过处理来方便地与异构化（PH催化量3 P）3的RhCl /丁基锂以得到活性乙烯基苷6，17和20以高收率。这些糖基供体已成功用于受体7、9和11的糖基化。在糖基供体6的情况下，二糖根据所选择的反应条件，可以以异头混合物形式或以高α-或β-选择性获得8、10和12。在每种情况下用糖基供体17和20的糖基化仅以高收率仅产生β-连接的产物。
• 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。