2,3,6-tri-O-acetyl-4-deoxy-4-fluoro-α-D-galactopyranosyl bromide | 148123-78-8

• 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: 2,3,6-tri-O-acetyl-4-deoxy-4-fluoro-α-D-galactopyranosyl bromide
• 英文别名: [(2R,3S,4R,5R,6R)-4,5-diacetyloxy-6-bromo-3-fluorooxan-2-yl]methyl acetate
• CAS: 148123-78-8
• 化学式: C₁₂H₁₆BrFO₇
• 分子量: 371.157
• InChiKey: ZOYLXCCDXVFFRQ-IIRVCBMXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  88.1
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  2,3,6-tri-O-acetyl-4-deoxy-4-fluoro-α-D-galactopyranosyl bromide 在 氰化汞 、 溶剂黄146 作用下， 以 硝基甲烷 、 苯 为溶剂， 反应 13.5h， 生成 benzyl 3-(2,3,6-tri-O-acetyl-4-deoxy-4-fluoro-β-D-galactopyranosyl)-2-deoxy-2-acetamido-α-D-galactopyranoside
  参考文献：
  名称：

  Synthesis of Fluorinated Mucin Core 2 Branched Oligosaccharides with the Potential of Novel Substrates and Enzyme Inhibitors for Glycosyltransferases and Sulfotransferases

  摘要：

  Syntheses of fluorinated mucin core 2 tri- and tetrasaccharides modified at the C-3 or C-4 position of the pertinent galactose residue are reported. These compounds were used for the study of sialyltransferases and 3-O-sulfotransferases involved in the biosynthesis of O-glycans. Our acceptor substrate specificity studies on three cloned sialyltransferases (Sia-Ts) revealed that a 3- or 4-fluoro substituent in, beta 1,4Gal resulted in poor acceptors for alpha 2,6(N)Sia-T and alpha 2,3(N)Sia-T, whereas 4-fluoro-Gal,beta 1,3GalNAc alpha was a good acceptor for alpha 2,3(O)Sia-T. Uniquely, 4-F-Gal,beta 1,4GlcNAc,beta 1,6(Gal,beta 1,3)GalNAc alpha-OBn was an inhibitor of alpha 2,6(N)Sia-T activity but not alpha 2,3(N)Sia-T activity. Further we found that the activities of only Gal 3-O-sulfotransferases and not sialyltransferases were adversely affected by a C-3 fluoro substituent at the other Gal terminal of mucin core 2. The strategy of building branched mucin core 2 structures by three glycosidation sequence coupling three classes of glycosyl donors with the reactivity-matching acceptors proved to be successful in syntheses of modified mucin-type core structures of O-glycan. The relative poor yields of the glycosylations using fluorinated galactosyl donors indicated that the fluorine modification dramatically decreased the donor reactivity due to electron-withdrawing effect.

  DOI：

  10.1021/jo052626j
• 作为产物：
  描述：

  1,2,3,6-tetra-O-acetyl-4-deoxy-4-fluoro-α-D-galactopyranose 在 氢溴酸 、 溶剂黄146 作用下， 反应 3.0h， 以94%的产率得到2,3,6-tri-O-acetyl-4-deoxy-4-fluoro-α-D-galactopyranosyl bromide
  参考文献：
  名称：

  An improved synthesis of 4-deoxy-4-fluoro-d-galactopyranosyl derivatives

  摘要：

  DOI：

  10.1016/0008-6215(93)80119-y

文献信息

• Stereoselective Synthesis of Fluorinated Galactopyranosides as Potential Molecular Probes for Galactophilic Proteins: Assessment of Monofluorogalactoside–LecA Interactions
  作者：Vincent Denavit、Danny Lainé、Chahrazed Bouzriba、Elena Shanina、Émilie Gillon、Sébastien Fortin、Christoph Rademacher、Anne Imberty、Denis Giguère

  DOI：10.1002/chem.201806197

  日期：2019.3.21

  galactophilic lectins. The first transverse relaxation‐optimized spectroscopy (TROSY) NMR experiments were performed on these interactions, examining chemical shift perturbations of the backbone resonances of LecA, a virulence factor from Pseudomonas aeruginosa. Moreover, taking advantage of the fluorine atom, the 19F NMR resonances of the monofluorogalactopyranosides were directly monitored in the presence

  六吡喃糖苷支架上的氟原子取代了羟基，可能会为研究各种生化过程提供宝贵的工具。作为正在进行的制备氟化碳水化合物的活动的一部分，对涉及一系列单氟化和多氟化吡喃半乳糖苷的合成和生物学评估的系统研究进行了描述。已经使用Chiron方法制备了各种单氟吡喃半乳糖苷，三氟和四氟吡喃半乳糖苷。考虑到文献中这些化合物的稀缺性，除了合成以外，还评估了它们的生物学特性。首先，与正常细胞相比，使用正常人和小鼠细胞研究了含氟化合物作为抗增殖剂。大多数氟化化合物均未显示出抗增殖活性。其次，这些碳水化合物探针被用作半乳凝集素的潜在抑制剂。对这些相互作用进行了首次横向弛豫优化光谱（TROSY）NMR实验，检查了LecA骨架毒性的化学位移扰动，这是一种毒力因子。铜绿假单胞菌。此外，利用氟原子，在存在和不存在LecA的情况下，直接监测单氟吡喃半乳糖苷的19 F NMR共振，以评估配体结合。最后，这些结果通过等温滴定量热法实验
• Selectively Deoxyfluorinated <i>N</i> ‐Acetyllactosamine Analogues as ¹⁹ F NMR Probes to Study Carbohydrate‐Galectin Interactions
  作者：Martin Kurfiřt、Martin Dračínský、Lucie Červenková Šťastná、Petra Cuřínová、Vojtěch Hamala、Michaela Hovorková、Pavla Bojarová、Jindřich Karban

  DOI：10.1002/chem.202101752

  日期：2021.9.9

  synthesized a complete series of six mono-deoxyfluorinated analogues of LacNAc, in which each hydroxyl has been selectively replaced by fluorine while the anomeric position has been protected as methyl β-glycoside. Initial evaluation of their binding to human galectin-1 and -3 by ELISA and 19F NMR T2-filter revealed that deoxyfluorination at C3, C4′ and C6′ completely abolished binding to galectin-1 but

  半乳糖凝集素是广泛表达的半乳糖结合凝集素，例如在免疫调节、转移扩散和病原体识别中暗示。N-乙酰乳糖胺（Galβ1-4GlcNAc、LacNAc）及其寡聚或糖基化形式是半乳糖凝集素的天然配体。为了探测半乳糖凝集素的底物特异性和结合模式，我们合成了完整系列的六种 LacNAc 单脱氧氟化类似物，其中每个羟基都被氟选择性取代，而异头位置被保护为甲基β-糖苷。通过 ELISA 和19 F NMR T 2初步评估它们与人半乳糖凝集素-1 和 -3 的结合-filter 显示 C3、C4' 和 C6' 处的脱氧氟化完全消除了与 galectin-1 的结合，但仍可检测到与 galectin-3 的非常弱的结合。此外，C2' 的脱氧氟化导致对 galectin-1 的结合亲和力增加了大约 8 倍，而与 galectin-3 的结合基本上不受影响。亲脂性测量表明，与 GlcNAc 部分的脱氧氟化作用相比，Gal
• Role of the galactosyl moiety of collagen glycopeptides for T-Cell stimulation in a model for rheumatoid arthritis
  作者：Björn Holm、Syed M. Baquer、Lotta Holm、Rikard Holmdahl、Jan Kihlberg

  DOI：10.1016/s0968-0896(03)00407-3

  日期：2003.9

  protected derivatives of beta-D-galactopyranosyl-5-hydroxy-L-lysine, in which HO-4 of galactose has been O-methylated or replaced by fluorine, have been prepared. The building blocks were incorporated at position 264 of the peptide fragment CII259-273 from type II collagen by solid-phase synthesis. The ability of these two glycopeptides, and two CII259-273 glycopeptides in which HO-4 of galactose was either

  制备了两种被保护的β-D-吡喃半乳糖基-5-羟基-L-赖氨酸衍生物，其中半乳糖的HO-4已被O-甲基化或被氟取代。通过固相合成将来自II型胶原蛋白的构建体掺入肽片段CII259-273的264位。然后确定了这两个糖肽和两个CII259-273糖肽（其中半乳糖的HO-4未修饰或被脱氧）引发类风湿性关节炎小鼠模型中T细胞杂交瘤反应的能力。杂交瘤均对CII259-273的β-D-半乳糖基残基的C-4修饰高度敏感，突出了HO-4作为T细胞受体重要接触点的作用。最有可能的，
• Effects of Sugar Functional Groups, Hydrophobicity, and Fluorination on Carbohydrate–DNA Stacking Interactions in Water
  作者：Ricardo Lucas、Pablo Peñalver、Irene Gómez-Pinto、Empar Vengut-Climent、Lewis Mtashobya、Jonathan Cousin、Olivia S. Maldonado、Violaine Perez、Virginie Reynes、Anna Aviñó、Ramón Eritja、Carlos González、Bruno Linclau、Juan C. Morales

  DOI：10.1021/jo402700y

  日期：2014.3.21

  Carbohydrate-aromatic interactions are highly relevant for many biological processes. Nevertheless, experimental data in aqueous solution relating structure and energetics for sugar-arene stacking interactions are very scarce. Here, we evaluate how structural variations in a monosaccharide including carboxyl, N-acetyl, fluorine, and methyl groups affect stacking interactions with aromatic DNA bases. We find small differences on stacking interaction among the natural carbohydrates examined. The presence of fluorine atoms within the pyranose ring slightly increases the interaction with the C-G DNA base pair. Carbohydrate hydrophobicity is the most determinant factor. However, gradual increase in hydrophobicity of the carbohydrate does not translate directly into a steady growth in stacking interaction. The energetics correlates better with the amount of apolar surface buried upon sugar stacking on top of the aromatic DNA base pair.
• US5612316A
  申请人：——

  公开号：US5612316A

  公开（公告）日：1997-03-18