methyl 3-O-benzyl-4,6-O-benzylidene-2-O-(2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl)-α-D-glucopyranoside | 118545-30-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: methyl 3-O-benzyl-4,6-O-benzylidene-2-O-(2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl)-α-D-glucopyranoside
• 英文别名: [(2R,3R,4S,5R,6S)-6-[[(2R,4aR,6S,7R,8S,8aR)-6-methoxy-2-phenyl-8-phenylmethoxy-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-7-yl]oxy]-3,4,5-tribenzoyloxyoxan-2-yl]methyl benzoate
• CAS: 118545-30-5
• 化学式: C₅₅H₅₀O₁₅
• 分子量: 950.993
• InChiKey: KFGIEIYWKOOYMJ-ISFNAELCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.7
• 重原子数：
  70
• 可旋转键数：
  20
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  170
• 氢给体数：
  0
• 氢受体数：
  15

反应信息

• 作为产物：
  描述：

  2,3,4,6-tetra-O-benzoylglucosyl bromide 在 2,6-二甲基吡啶 、 gold(III) bromide 、 4 A molecular sieve 、 四丁基碘化铵 作用下， 以 二氯甲烷 为溶剂， 反应 58.0h， 生成 methyl 3-O-benzyl-4,6-O-benzylidene-2-O-(2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl)-α-D-glucopyranoside
  参考文献：
  名称：

  Propargyl 1,2-orthoesters as glycosyl donors: stereoselective synthesis of 1,2-trans glycosides and disaccharides

  摘要：

  Propargyl 1,2-orthoesters are identified as glycosyl donors. Various glycosides and disaccharides were synthesized in a stereoselective manner using AuBr3 as the promoter. AuBr3 may activate the alkyne resulting in the formation of a 1,2-dioxolenium ion and also behaves as a Lewis acid to facilitate the attack of the glycosyl acceptor. The versatility of the protocol was demonstrated using a panel of aglycones comprising aliphatic, alicyclic, steroidal and sugar alcohols. (C) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2007.07.015

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。
• <i>N</i> -Trifluoromethylthiosaccharin/TMSOTf: A New Mild Promoter System for Thioglycoside Activation
  作者：Cian Mc Carthy、Matthias Tacke、Xiangming Zhu

  DOI：10.1002/ejoc.201900265

  日期：2019.4.30

  N‐Trifluoromethylthiosaccharin was used to activate a series of thioglycosides in the presence of catalytic amounts of TMSOTf. Chemoselective activation of ethyl thioglycosides in the presence of phenyl thioglycosides was also achieved under the same conditions.

  在催化量的TMSOTf存在下，N-三氟甲基硫代糖精用于活化一系列硫糖苷。在相同条件下，在苯基硫代糖苷的存在下，也能实现乙基硫代糖苷的化学选择性活化。
• A New, Powerful Glycosylation Method:  Activation of Thioglycosides with Dimethyl Disulfide−Triflic Anhydride
  作者：János Tatai、Péter Fügedi

  DOI：10.1021/ol702139u

  日期：2007.10.1

  Dimethyl disulfide reacts with triflic anhydride to provide a highly reactive electrophile. Various thioglycosides, differing in their thio aglycons, carbohydrate units, and protecting group pattern, were activated with Me2S2-Tf2O in the presence of different glycosyl acceptors. The reactions proceeded at low temperatures within a short time, affording oligosaccharides in high yields both on primary

  二甲基二硫化物与三氟甲磺酸酐反应以提供高反应活性的亲电子试剂。在存在不同糖基受体的情况下，用Me2S2-Tf2O激活了各种硫代糖苷，它们的硫苷元，糖类单元和保护基团模式不同。反应在短时间内在低温下进行，伯羟基和仲羟基均以高收率得到寡糖。武装和解除武装的糖基供体被同样有效地激活。
• Alkyl sulfenyl triflate as activator in the thioglycoside-mediated formation of β-glycosidic linkages during oligosaccharide synthesis
  作者：Falguni Dasgupta、Per J. Garegg

  DOI：10.1016/0008-6215(88)85071-7

  日期：1988.6

  Synthese de disaccharides par couplage d'un thioglycoside et d'un glycoside en presence de bromure d'acide nitro-2 benzenesulfinique ou de methylsulfenyl triflate

  存在于酰胺基硝基二硝基苯磺酸或三氟甲磺酸甲基亚砜中的双糖合成糖苷和糖苷
• GeCl₂·Dioxane–AgBF₄ Catalyzed Activation of Glycosyl Fluorides for Glycosylation
  作者：Qiuyu Zhu、Yu Tang、Biao Yu

  DOI：10.1021/acs.orglett.2c01146

  日期：2022.5.27

  catalytic glycosyl fluoride activation system using the GeCl2·dioxane–AgBF4 combination was developed, which involves a reversible activation of the anomeric C–F bond by a [Ge(II)–Cl]+ cation and a reversible chloride ion transfer between Ge(II) and glycosyl cations. This catalytic glycosylation system is easy to operate, proceeds at room temperature, and offers a broad scope of substrates.

  开发了一种使用 GeCl 2 ·二恶烷-AgBF 4组合的催化糖基氟化物活化系统，该系统涉及通过 [Ge(II)-Cl] +阳离子对异头 C-F 键的可逆活化和在它们之间的可逆氯离子转移。 Ge(II) 和糖基阳离子。这种催化糖基化系统易于操作，在室温下进行，并提供广泛的底物。