苯基2-O-乙酰基-3,4,6-三-O-苯甲基-1-硫-β-D-半乳吡喃糖苷 | 183875-28-7

• 物质功能分类: 医药中间体 - 吡喃类化合物
• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 苯基2-O-乙酰基-3,4,6-三-O-苯甲基-1-硫-β-D-半乳吡喃糖苷
• 英文名称: phenyl 2-O-acetyl-3,4,6-tri-O-benzyl-1-thio-β-D-galactopyranoside
• 英文别名: Gal[2Ac,346Bn]-beta-SPh；[(2S,3R,4S,5S,6R)-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)-2-phenylsulfanyloxan-3-yl] acetate
• CAS: 183875-28-7
• 化学式: C₃₅H₃₆O₆S
• 分子量: 584.733
• InChiKey: IKFDEPUTIUTSLC-NVCPMKERSA-N

物化性质

• 熔点：
  111°C(lit.)
• 沸点：
  691.3±55.0 °C(Predicted)
• 密度：
  1.23±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  42
• 可旋转键数：
  14
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  88.5
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  苯基2-O-乙酰基-3,4,6-三-O-苯甲基-1-硫-β-D-半乳吡喃糖苷 在 2,6-二叔丁基-4-甲基吡啶 、 ammonium cerium(IV) nitrate 、 4 A molecular sieve 、 sodium methylate 、 silver trifluoromethanesulfonate 、 氯 、 sodium hydride 、 三苯基膦 作用下， 以 甲醇 、 四氯化碳 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 98.58h， 生成 phenyl [3,4,6-tri-O-benzyl-α-D-galactopyranosyl]-(1->3)-(2-acetamido-4,6-di-O-acetyl-2-deoxy-α-D-glucopyranosyl)-(1->3)-2-O-benzoyl-4-O-benzyl-1-thio-α-L-rhamnopyranoside
  参考文献：
  名称：

  Synthesis of Glycoconjugate Vaccines against Shigella dysenteriae Type 1

  摘要：

  Syntheses of a hexadecasaccharide and smaller fragments corresponding to one-four repeating units of the O-specific polysaccharide of Shigella dysenteriae type 1 are reported in a reactive aglyconlinked from. Two tetrasaccharide donor/acceptor repeating units were assembled from monosaccharide precursors in a stepwise fashion and used in a linear, iterative manner to construct the higher-membered saccharides using Schmidt's glycosylation technique that proved superior to others tested. Single-point attachment of the saccharides to human serum albumin, using a secondary heterobifunctional spacer, afforded a range of glycoconjugates for a detailed evaluation of their immunological characteristics.

  DOI：

  10.1021/jo980660a
• 作为产物：
  描述：

  2,3,5-三邻苄基-1-o-(4-硝基苯甲酰基)-d-阿拉伯呋喃糖 、 苯硫酚 在 mercury dibromide 作用下， 以 乙腈 为溶剂， 反应 24.0h， 以80%的产率得到苯基2-O-乙酰基-3,4,6-三-O-苯甲基-1-硫-β-D-半乳吡喃糖苷
  参考文献：
  名称：

  Prearranged Glycosides. Part 8. Intramolecular α-Galactosylation Via Succinoyl Tethered Glycosides

  摘要：

  Benzyl protected phenyl 1-thio-galactopyranoside donors which were tethered by a succinoyl linker at their positions 2 and 6, respectively, to position 3 of a blocked benzyl glucopyranoside acceptor with a 4-OH group solely afforded the corresponding alpha-(1-->4)-linked disaccharides upon intramolecular glycosylation. 4,6-Siloxane protected mannosides react with rearrangement of the siloxane group under similar conditions.

  DOI：

  10.1080/07328309908544056

文献信息

• Generalizing Glycosylation:  Synthesis of the Blood Group Antigens Le^a, Le^b, and Le^x Using a Standard Set of Reaction Conditions
  作者：Lin Yan、Daniel Kahne

  DOI：10.1021/ja9608555

  日期：1996.1.1

  glycosylation method under one set of reaction conditions. In this paper, we show that the sulfoxide glycosylation method can be used to form all of the glycosidic linkages in the Lewis blood group antigens Lea (1), Leb (2), and Lex (3) stereoselectively under a uniform set of reaction conditions. This work highlights the flexibility of the sulfoxide method and demonstrates its utility for constructing families

  由于任何糖基化方法都没有通用的反应条件，因此世界上只有少数实验室才能制造出具有生物学意义的寡糖。为了让非专业人士也能合成碳水化合物，关键是要有一种糖基化方法，可以在单一条件下在多种情况下发挥作用。由于结构复杂，Lewis 血型抗原引起了许多合成碳水化合物组的注意。尽管它们已被多次合成，但从未在一组反应条件下使用单一糖基化方法制备它们。在本文中，我们表明亚砜糖基化方法可用于形成路易斯血型抗原 Lea (1)、Leb (2)、和 Lex (3) 在一组统一的反应条件下立体选择性地进行。这项工作突出了亚砜方法的灵活性，并证明了其在构建相关族中的效用...
• Synthesis of Superarmed Thioglycosides via the Ring Opening of 1,2-Orthoesters
  作者：Xiangming Zhu、Zoe Beato

  DOI：10.1055/a-2132-1938

  日期：2023.12

  2-trans stereochemistry, and importantly, makes use of trimethylsilyl thioethers as sulfur nucleophiles to avoid the use of unpleasant free thiols. Ten examples of ethyl and phenyl thioglycosides of mono- and disaccharides were synthesised from their orthoesters using tris(pentafluorophenyl)borane (BCF) as the Lewis acid promoter and were obtained in good yield and purity.

  自从武装-解除武装策略出现以来，硫代糖苷已成为一锅寡糖合成的重要工具。此后，糖基供体反应性的连续体已扩展到包括所谓的“超级”硫代糖苷供体，其反应性不仅仅依赖于保护基团的诱导效应。在这里，我们报告了一种通过 1,2-原酸酯开环合成超级硫代糖苷的新方法。该方法确保了必要的 1,2-反式立体化学，重要的是，利用三甲基甲硅烷基硫醚作为硫亲核试剂，以避免使用令人不快的游离硫醇。
• [R₄N] [AOT]: A Surfactant Ionic Liquid as a Mild Glycosylation Promoter
  作者：M. Carmen Galan、Anh Tuan Tran、Julien Boisson、David Benito、Craig Butts、Julian Eastoe、Paul Brown

  DOI：10.1080/07328303.2011.609626

  日期：2011.9.1

  [RN4][AOT] is a versatile surfactant ionic liquid that can be used in combination with N-Iodosuccinimide to promote the room temperature glycosylation of thiophenyl glycoside donors. The conditions are mild, with no requirement for molecular sieves, and are compatible with a wide range of donors and protecting groups. Under these conditions, a different range of disaccharides have been obtained in good to excellent yields and good stereoselectivities. Furthermore, the anomeric outcome of the glycosylation reaction using glycosyl donors with no participating group at C-2 could be tuned by switching the solvent from DCM to MeCN.
• Screening for Galectin-3 Inhibitors from Synthetic Lacto-<i>N</i>-biose Libraries Using Microscale Affinity Chromatography Coupled to Mass Spectrometry
  作者：Sébastien Fort、Hyo-Sun Kim、Ole Hindsgaul

  DOI：10.1021/jo060485v

  日期：2006.9.1

  The synthesis and screening of two beta-D-Galp-(1-3)-beta-D-GlcpN ( lacto-N-biose) disaccharide libraries are reported. Solution-phase synthetic modifications at the HO-2' and NH positions were performed in an effort to enhance the affinity toward galectin-3, a galactose-binding protein involved in tumor metastasis, apoptosis, and inflammation. The libraries were screened for galectin-3 binding by microscale frontal affinity chromatography coupled to mass spectrometry ( FAC/MS) allowing for rapid ranking of the different inhibitors and the determination of the galectin-3 binding K-d's. Compounds bearing a hydrophobic substituent on the NH group showed the highest affinity for the lectin. The N-naphthoyl derivative ( K-d = 10.6 mu M) was the best inhibitor with a 7 times increased affinity as compared to the N-acetyl parent compound ( K-d = 73.3 mu M).