methyl (2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl)-(1->6)-(2,3,4-tri-O-benzoyl-β-D-glucopyranosyl)-(1->6)-2,3,4-tri-O-benzyl-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 (2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl)-(1->6)-(2,3,4-tri-O-benzoyl-β-D-glucopyranosyl)-(1->6)-2,3,4-tri-O-benzyl-α-D-glucopyranoside
• 英文别名: methyl 2,3,4-tri-O-benzyl-6-O-(2,3,4-tri-O-benzoyl-6-O-(2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl)-α-D-glucopyranosyl)-β-D-glucopyranoside；methyl (2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl)-(1→6)-(2,3,4-tri-O-benzoyl-β-D-glucopyranosyl)-(1→6)-2,3,4-tri-O-benzyl-α-D-glucopyranoside；methyl 2,3,4,6-tetra-O-benzoyl-β-D-glucopyranoside-(1→6)-2,3,4-tri-O-benzoyl-β-D-glucopyranoside-(1→6)-2,3,4-tri-O-benzyl-α-D-glucopyranoside；methyl 2,3,4-tri-O-benzyl-6-O-[2,3,4-tri-O-benzoyl-6-O-(2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl)-β-D-glucopyranosyl]-α-D-glucopyranoside；Bz(-2)[Bz(-3)][Bz(-4)][Bz(-6)]Glc(b1-6)[Bz(-2)][Bz(-3)][Bz(-4)]Glc(b1-6)[Bn(-2)][Bn(-3)][Bn(-4)]a-Glc1Me；[(2R,3R,4S,5R,6R)-3,4,5-tribenzoyloxy-6-[[(2R,3R,4S,5R,6R)-3,4,5-tribenzoyloxy-6-[[(2R,3R,4S,5R,6S)-6-methoxy-3,4,5-tris(phenylmethoxy)oxan-2-yl]methoxy]oxan-2-yl]methoxy]oxan-2-yl]methyl benzoate
• 化学式: C₈₉H₈₀O₂₃
• 分子量: 1517.6
• InChiKey: VPIZLDSRECVXRZ-BBGJTGAFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  14.8
• 重原子数：
  112
• 可旋转键数：
  38
• 环数：
  13.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  267
• 氢给体数：
  0
• 氢受体数：
  23

反应信息

• 作为产物：
  描述：

  甲基2,3,4-三-O-苄基-α-D-吡喃葡萄糖苷 、 在 trifluoromethanesulfonyloxy(triphenylphosphine)gold(I) 、 三氟甲磺酸 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 以93%的产率得到methyl (2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl)-(1->6)-(2,3,4-tri-O-benzoyl-β-D-glucopyranosyl)-(1->6)-2,3,4-tri-O-benzyl-α-D-glucopyranoside
  参考文献：
  名称：

  金（I）催化的糖基壬二酸酯作为供体的糖基化

  摘要：

  开发了一种简单且通用的糖基化方法，其中武装和解除武装的糖基炔诺酸酯都作为供体。在有或没有TfOH的辅助下采用金（I）配合物作为催化剂，本糖基化方案的范围非常宽。通过潜在的活性策略和多重正交一锅策略在低聚糖的有效合成中证明了本发明的炔酸供体的实用性。最后，该方法能够正式合成肺炎链球菌血清型3的四糖半抗原和32mer聚甘露糖苷的高度收敛合成。

  DOI：

  10.1021/acs.orglett.9b03851

文献信息

• NIS/TMSOTf-Promoted Glycosidation of Glycosyl <i>ortho</i>-Hexynylbenzoates for Versatile Synthesis of <i>O</i>-Glycosides and Nucleosides
  作者：Rongkun Liu、Qingting Hua、Qixin Lou、Jiazhe Wang、Xiaona Li、Zhi Ma、You Yang

  DOI：10.1021/acs.joc.1c00151

  日期：2021.3.19

  approach with glycosyl ortho-hexynylbenzoates as donors for the highly efficient synthesis of O-glycosides and nucleosides. The glycosidation approach highlights the merits of mild reaction conditions, cheap promoters, extremely wide substrate scope, and good to excellent yields. Notably, the glycosidation approach performs very well in the construction of a series of challenging O- and N-glycosidic

  糖苷化在介导多种生物学过程的O-糖苷和核苷的合成中起着关键作用。然而，就糖苷化产率，温和的反应条件，容易获得的糖基供体和廉价的启动子而言，用于合成O-糖苷和核苷的有效糖苷化方法仍然具有挑战性。在这里，我们报告了一种多功能的N-碘琥珀酰亚胺/三氟甲磺酸三甲基甲硅烷基酯（NIS / TMSOTf）促进的糖苷化方法，其中糖基邻-己炔基苯甲酸酯为高效合成O的供体-糖苷和核苷。糖苷化方法强调了温和反应条件，廉价的启动子，极其广泛的底物范围以及良好至优异的收率的优点。值得注意的是，糖苷化方法在一系列具有挑战性的O-和N-糖苷键的构建中表现非常出色。然后通过一锅策略和逐步策略将糖苷化方法应用于寡糖的有效合成。在分离和表征离去基团的离去物种的基础上，提出了一个合理的机理，即NIS / TMSOTf促进了糖基邻己基苯甲酸酯的糖基化。
• MPTGs: Thioglycoside Donors for Acid-Catalyzed <i>O</i>-Glycosylation and Latent-Active Synthetic Strategies
  作者：Shaofu Du、Justin R. Ragains

  DOI：10.1021/acs.orglett.8b03958

  日期：2019.2.15

  range of alcohol acceptors in the presence of 10 mol % of triflic acid at room temperature. Particularly encouraging is the reactivity of MPTGs toward unreactive acceptors. MPTGs can be synthesized from the requisite vinyl bromides using the Suzuki reaction, and this chemistry can be leveraged toward a “latent-active” strategy for oligosaccharide synthesis.

  在室温下，在10摩尔％的三氟甲磺酸存在下，4-（对甲氧基苯基）-4-戊烯基硫代糖苷（MPTG）经过一系列醇受体的酸催化O-糖基化。特别令人鼓舞的是MPTG对非反应性受体的反应性。可以使用Suzuki反应从必需的乙烯基溴化物中合成MPTG，并且可以将这种化学方法用于寡糖合成的“潜在活性”策略。
• Chemoselective Glycosylations. 2. Differences in Size of Anomeric Leaving Groups Can Be Exploited in Chemoselective Glycosylations
  作者：Richard Geurtsen、Duncan S. Holmes、Geert-Jan Boons

  DOI：10.1021/jo971233k

  日期：1997.11.1

  We have developed a novel chemoselective glycosylation strategy. This glycosylation strategy is based on the fact that the glycosyl reactivity of an anomeric thiol group can be controlled by the bulkiness of this group whereby we have produced a new range of differentially reactive coupling substrates. It was also shown that the anomeric configuration of the thioglycosides affects the reactivity of

  我们已经开发出一种新颖的化学选择性糖基化策略。这种糖基化策略基于以下事实：异头硫醇基团的糖基反应性可以通过该基团的庞大性来控制，由此我们生产了一系列新的差异反应性偶联底物。还显示出硫糖苷的异头构型影响底物的反应性。新方法将使具有生物学重要性的复杂寡糖能够以高度融合的方式制备。这种方法的多功能性是由结构单元7、9、10、12和14合成五糖34而无需进行单个保护基操作即可证明的。
• Orthogonal One-Pot Synthesis of Oligosaccharides Based on Glycosyl<i>ortho</i>-Alkynylbenzoates
  作者：Yunqin Zhang、Guisheng Xiang、Shaojun He、Yikao Hu、Yanjun Liu、Lili Xu、Guozhi Xiao

  DOI：10.1021/acs.orglett.9b00617

  日期：2019.4.5

  of the most popular one-pot glycosylation strategies is orthogonal one-pot synthesis, which was mainly based on thioglycosides. Despite its successful application, shortcomings of thioglycosides including aglycon transfers, interference of departing species and unpleasant odor restrict its application scope. Herein, we report a new and efficient orthogonal one-pot synthesis of oligosaccahrides based

  正交一锅合成是最流行的一锅糖基化策略之一，其主要基于硫代糖苷。尽管已成功应用，但是硫糖苷的缺点包括糖苷配基转移，离去物种的干扰和难闻的气味限制了其应用范围。在本文中，我们报告了一种基于糖基邻炔基苯甲酸酯的新型高效正交一锅合成寡糖的方法，解决了基于硫代糖苷的正交一锅合成的问题。通过这种方法已经有效地合成了十几种寡糖。
• Investigation of the reactivity difference between thioglycoside donors with variant aglycon parts
  作者：Martina Lahmann、Stefan Oscarson

  DOI：10.1139/v02-101

  日期：2002.8.1

  The reactivity of perbenzoylated thioglycosides with various thiol aglycons has been compared and quantified using competitive glycosylation experiments. Methyl 2,3,4-tri-O-benzyl-α-D-glucopyranoside was employed as acceptor and DMTST as a promoter. The reactivity was found, as expected, to depend on the electron donating properties of the aglycon. Hence, the most reactive donor, the cyclohexyl thioglycoside, was found to be about three times as reactive as the thioethyl glycoside, which in turn was twice as reactive as the thiomethyl donor. The thiophenyl donor was even less reactive, whereas p-halophenyl donors were inert under the glycosylation conditions used — but could be activated using NIS–TfOH as promoter. Furthermore, it was found that galactosyl donors were three to four times more reactive than the corresponding glucosyl derivative. These results allowed the design of an orthogonal coupling between thioglycosides with the same protecting groups (benzoyls) but with different thiol aglycons. Key words: thioglycosides, orthogonal glycosylations, competititive glycosylations.

  已苯酰化硫代糖苷与不同硫醇配基的反应性进行了比较和定量化，使用竞争性糖基化实验。甲基2,3,4-三-O-苄基-α-D-葡萄糖吡喃糖苷被用作受体，DMTST被用作促进剂。如预期，发现反应性取决于硫配基的电子给予性质。因此，最具反应性的供体环己硫代糖苷发现比硫乙基糖苷反应性高约三倍，后者又比硫甲基供体反应性高出两倍。硫苯供体反应性更低，而对p-卤苯供体在糖基化条件下是惰性的，但可以使用NIS-TfOH作为促进剂激活。此外，发现半乳糖供体比相应的葡萄糖衍生物反应性高三到四倍。这些结果为设计具有相同保护基（苯酰基）但具有不同硫醇配基的硫代糖苷之间的正交偶联提供了可能。关键词：硫代糖苷，正交糖基化，竞争性糖基化。