6-O-acetyl-2,3,4-tri-O-benzyl-α-D-glucopyranosyl iodide | 441017-58-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6-O-acetyl-2,3,4-tri-O-benzyl-α-D-glucopyranosyl iodide
• 英文别名: [(2R,3R,4S,5R,6R)-6-iodo-3,4,5-tris(phenylmethoxy)oxan-2-yl]methyl acetate
• CAS: 441017-58-9
• 化学式: C₂₉H₃₁IO₆
• 分子量: 602.466
• InChiKey: QTXKQFOIFYCGKT-RQKPWJHBSA-N

物化性质

• 沸点：
  629.8±55.0 °C(Predicted)
• 密度：
  1.43±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  36
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.34
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  6-O-acetyl-2,3,4-tri-O-benzyl-α-D-glucopyranosyl iodide 在 吡啶 、 20 % Pd(OH)2/C 、 氢气 、 四丁基碘化铵 、 溶剂黄146 、 2,4,6-三叔丁基嘧啶 作用下， 以 甲醇 、 乙酸乙酯 、 甲苯 为溶剂， 50.0~55.0 ℃ 、482.64 kPa 条件下， 反应 132.0h， 生成 (1S,2R,8R,8aR)-2,8-bis(acetoxy)-1-(2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyloxy)-hexahydroindolizin-5(1H)-one
  参考文献：
  名称：

  Fleetamine (3-O-α-d-glucopyranosyl-swainsonine): the synthesis of a hypothetical inhibitor of endo-α-mannosidase

  摘要：

  3-O-alpha-D-Glucopyranosyl-swainsonine was originally proposed(17) as a potential inhibitor of the mammalian enzyme endo-alpha-mannosidase, but its synthesis has not been reported. Herein we report the total synthesis of this enigmatic compound, utilizing a halide-ion catalysed glycosylation of a swainsonine lactam with a glucosyl iodide donor as the key step. The resulting inhibitor was evaluated as an inhibitor of human endo-alpha-mannosidase, and as a ligand for bacterial orthologs from Bacteroides thetaiotaomicron and Bacteroides xylanisolvens, including active-centre variants, although no evidence for binding or inhibition was observed. The surprising lack of binding was rationalized by using structural alignment with an endo-alpha-mannosidase inhibitor complex, which identified deleterious interactions with the swainsonine piperidine ring and an essential active site residue. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2012.06.011
• 作为产物：
  描述：

  甲基 2,3,4,6-O-四苄基-alpha-D-吡喃葡萄糖苷 在 碘代三甲硅烷 、 zinc(II) chloride 作用下， 以 二氯甲烷 、 溶剂黄146 为溶剂， 生成 6-O-acetyl-2,3,4-tri-O-benzyl-α-D-glucopyranosyl iodide
  参考文献：
  名称：

  Solution-Phase Hexasaccharide Synthesis Using Glucosyl Iodides

  摘要：

  [GRAPHIC]Oligosaccharides composed of 1,6-glucosyl residues have been prepared from glucosyl iodides. The reactions are highly stereoselective, giving the a-glycosides as the only isolated products in yields ranging from 84% to 94%. Oligomer synthesis can take place in an iterative 1 + 1 + 1 fashion or in a convergent manner where dimer iodides serve as donors for higher order acceptors.

  DOI：

  10.1021/ol025887d

文献信息

• Regioselective Acetolysis of Highly<i>O</i>-Benzylated Carbohydrates Promoted by Iodine or an Iodine/Silane Combined Reagent: Use of Isopropenyl Acetate as an Alternative to Acetic Anhydride
  作者：Maddalena Giordano、Alfonso Iadonisi、Antonello Pastore

  DOI：10.1002/ejoc.201300064

  日期：2013.5

  the protocols presented here do not suffer from the use of harsh acidic reagents and excess amounts of high-boiling acetic anhydride. The activation of IPA with iodine and triethylsilane (or the cheaper polymethylhydrosiloxane, PMHS) usually results in shorter reaction times, with the acetolysis occurring preferentially (with some exceptions) at primary benzyloxy groups. With anomerically armed sugars

  聚-O-苄基化糖的区域选择性乙酰解脱-O-苄基化可以通过用碘/硅烷组合试剂或单独的碘激活乙酸异丙烯酯(IPA)来触发。与其他已知的乙酰化程序不同，此处介绍的协议不会受到使用强酸试剂和过量高沸点乙酸酐的影响。用碘和三乙基硅烷（或更便宜的聚甲基氢硅氧烷，PMHS）活化 IPA 通常会导致更短的反应时间，丙酮分解优先（有一些例外）发生在伯苄氧基。对于异头武装的糖，异头碘化可以是一个伴随的过程，以产生高反应性的中间体，在合适的淬火条件下，这些中间体可以原位转化为可用的和有用的结构单元。另一方面，单独用碘激活 IPA 可使反应在较温和的条件下发生，尽管时间较长。在几乎所有报道的例子中，IPA 可以适度过量使用（5 当量），但它作为溶剂的使用对于氨基糖模型化合物至关重要，否则对任何乙酰化修饰都是顽固的。这些条件的另一个优势在于前所未有的可能性，将乙酰化步骤纳入一锅合成序列，导致糖类底物的多种功能修饰。
• Structural and Kinetic Dissection of the<i>endo</i>-α-1,2-Mannanase Activity of Bacterial GH99 Glycoside Hydrolases from<i>Bacteroides</i> spp.
  作者：Zalihe Hakki、Andrew J. Thompson、Stephanie Bellmaine、Gaetano Speciale、Gideon J. Davies、Spencer J. Williams

  DOI：10.1002/chem.201405539

  日期：2015.1.26

  Glycoside hydrolase family 99 (GH99) was created to categorize sequence‐related glycosidases possessing endo‐α‐mannosidase activity: the cleavage of mannosidic linkages within eukaryotic N‐glycan precursors (Glc1–3Man9GlcNAc2), releasing mono‐, di‐ and triglucosylated‐mannose (Glc1–3‐1,3‐Man). GH99 family members have recently been implicated in the ability of Bacteroides spp., present within the gut

  糖苷水解酶家族99（GH99）的创建是为了对具有内切α-甘露糖苷酶活性的序列相关糖苷酶进行分类：真核N-聚糖前体（Glc 1-3 Man 9 GlcNAc 2）中甘露糖苷键的裂解，释放单，双-和triglucosylated甘露糖（GLC 1-3 -1,3-曼）。GH99家族成员最近与拟杆菌的能力有关 spp.spp。，存在于肠道菌群内，通过分解分支内的αMan-1,3-αMan→1,2-αMan-1,2-αMan序列来代谢真菌细胞壁α-甘露聚糖，从而释放α-1,3-甘露二糖偏离主要的α-1,6-甘露聚糖骨架。我们报告了一系列底物和抑制剂的开发，我们将其用于在动力学和结构上表征细菌拟南芥（Theactotaides thetaiotaomicron）和xylanisolvens的细菌GH99酶的这种新型内-α-1,2-甘露聚糖酶活性。这些数据表明大约为5 kJ mol -1对-2子位点中相
• Synthesis of the tetrasaccharide α-d-Glcp-(1→3)-α-d-Manp-(1→2)-α-d-Manp-(1→2)-α-d-Manp recognized by Calreticulin/Calnexin
  作者：Emiliano Gemma、Martina Lahmann、Stefan Oscarson

  DOI：10.1016/j.carres.2005.09.001

  日期：2005.11

  The title compound as its methyl glycoside was efficiently synthesized using a block synthesis approach. Halide-assisted glycosidations between 6-O-acetyl-2,3,4-tri-O-benzyl-alpha-D-glucopyranosyl iodide and ethyl 2-O-acetyl-4,6-di-O-benzyl-1-thio-alpha-D-mannopyranoside using triphenylphosphine oxide as promoter yielded, with complete alpha-selectivity, a disaccharide building block in high yield. The

  使用嵌段合成方法有效地合成了标题化合物作为其甲基糖苷。6-O-乙酰基-2,3,4-三-O-苄基-α-D-吡喃葡萄糖基碘化物与乙基2-O-乙酰基-4,6-二-O-苄基-1-硫代烃之间的卤化物辅助糖基化使用三苯基氧化膦作为促进剂的β-α-D-甘露吡喃糖苷以完全的α-选择性产生了高产率的二糖结构单元。事实证明，该化合物的过苄基化衍生物是出色的供体，它以NIS / AgOTf促进的偶联方式提供88％的受保护目标四糖与已知的甲基二甘露糖苷受体。然后通过催化氢解脱保护得到目标化合物，总产率为47％。
• Chemical Synthesis and Evaluation of Exopolysaccharide Fragments Produced by &lt;i&gt;Leuconostoc mesenteroides&lt;/i&gt; Strain NTM048
  作者：Shinsuke Inuki、Hitomi Tabuchi、Chiaki Matsuzaki、Yasunori Yonejima、Keiko Hisa、Ikuo Kimura、Kenji Yamamoto、Hiroaki Ohno

  DOI：10.1248/cpb.c21-00919

  日期：2022.2.1

  bacteria, fungi and algae. Some EPSs have intriguing biological properties such as anticancer and immunomodulatory activities. Our group has recently found that EPSs generated from Leuconostoc mesenteroides ssp. mesenteroides strain NTM048 (NTM048 EPS) enhanced a production of mucosal immunoglobulin A (IgA) of mouse. Herein, we described the synthesis and evaluation of the tetrasaccharide fragments of

  胞外多糖 (EPS) 广泛存在于由细菌、真菌和藻类制成的天然产物中。一些 EPS 具有有趣的生物学特性，例如抗癌和免疫调节活性。我们小组最近发现由Leuconostoc mesenteroides ssp 产生的 EPS。mesenteroides菌株 NTM048 (NTM048 EPS) 增强了小鼠黏膜免疫球蛋白 A (IgA) 的产生。在这里，我们描述了 NTM048 EPS 四糖片段的合成和评估，以获得有关负责 IgA 诱导活性的分子机制的信息。 全尺寸图像
• Glycosyl iodides. History and recent advances
  作者：Peter J. Meloncelli、Alan D. Martin、Todd L. Lowary

  DOI：10.1016/j.carres.2009.02.032

  日期：2009.6

  The use of glycosyl iodides as an effective method for the preparation of glycosides has had a recent resurgence in carbohydrate chemistry, despite its early roots in which these species were believed to be of limited use. Renewed interest in these species as glycosylating agents has been spurred by their demonstrated utility in the stereoselective preparation of O-glycosides, and other glycosylic compounds. This review provides a brief historical account followed by an examination of the use of glycosyl iodides in the synthesis of oligosaccharicles and other glycomimetics, including C-glycosylic compounds, glycosyl azides and N-glycosides. (C) 2009 Elsevier Ltd. All rights reserved.