1,3,4,6-tetra-O-acetyl-2-deoxy-2-fluoromannopyranose | 141395-49-5

• 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: 1,3,4,6-tetra-O-acetyl-2-deoxy-2-fluoromannopyranose
• 英文别名: 2-Deoxy-2-fluoro-D-mannopyranose Tetraacetate；[(2R,3R,4S,5S)-3,4,6-triacetyloxy-5-fluorooxan-2-yl]methyl acetate
• CAS: 141395-49-5
• 化学式: C₁₄H₁₉FO₉
• 分子量: 350.298
• InChiKey: KIPRSJXOVDEYLX-DYPLGBCKSA-N

物化性质

• 沸点：
  404.2±45.0 °C(Predicted)
• 密度：
  1.30±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  24
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  114
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  1,3,4,6-tetra-O-acetyl-2-deoxy-2-fluoromannopyranose 在 camphor-10-sulfonic acid 、 三氟化硼乙醚 、 sodium methylate 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 18.0h， 生成 phenyl 4,6-O-benzylidene-2-deoxy-2-fluoro-1-thio-α-D-mannopyranoside
  参考文献：
  名称：

  4,6-O-Benzylidene-Directed β-Mannopyranosylation and α-Glucopyranosylation:  The 2-Deoxy-2-fluoro and 3-Deoxy-3-fluoro Series of Donors and the Importance of the O2−C2−C3−O3 Interaction

  摘要：

  A series of 4,6-O-benzylidene-protected 2-O-benzyl-3-deoxy-3-fluoro- and 3-O-benzyl-2-deoxy-2-fluorogluco- and mannopyranosyl thioglycosides were synthesized and their coupling reactions with a series of alcohols, on preactivation with 1-benzenesulfinylpiperidine and trifluoromethanesulfonic anhydride, investigated. In all cases, the selectivities were lower than those observed with the corresponding simple 4,6-O-benzylidene 2,3-di-O-benzylgluco- and mannopyranosyl thioglycosides. This leads to the conclusion that the high beta-selectivity observed with 4,6-O-benzylidene 2,3-di-O-benzylmannopyranosyl donors under the same conditions is in large part derived from the compression of the O2-C2-C3-O3 torsion angle on going from the intermediate covalent glycosyl triflate to the oxacarbenium ion, as compared to the relaxation of this torsion angle in the gluco series.

  DOI：

  10.1021/jo062294y
• 作为产物：
  描述：

  2-deoxy-2-fluoro-2,3:5,6-di-O-isopropylidene-aldehydo-D-glucose 在 吡啶 、 三氟乙酸 作用下， 反应 0.08h， 生成 1,3,4,6-tetra-O-acetyl-2-deoxy-2-fluoromannopyranose
  参考文献：
  名称：

  1,2-脱水-3,4：5,6-二-O-异亚丙基-1-C-硝基-d-甘露糖醇与氟化氢钾在乙二醇中的反应：2-脱氧-2-氟-d的合成-葡萄糖

  摘要：

  1,2-脱水-3,4：5,6-二-O-异亚丙基-1-C-硝基-d-甘露醇（2）与乙二醇中的氟化氢钾在无水条件下的反应为生成2-脱氧-2-氟-d-葡萄糖，其18F标记的类似物是用于医学成像的重要放射性药物。该反应在较小程度上伴随着最初形成的氟醛在C-2处的差向异构化，并且还会导致溶剂在C-2中发生攻击。

  DOI：

  10.1016/s0008-6215(00)90137-x

文献信息

• Process for preparing nucleotide inhibitors of glycosyltransferases
  申请人：The Scripps Research Institute

  公开号：US05770407A1

  公开（公告）日：1998-06-23

  Nucleotide linked 2-deoxy-2-fluoroglycosides are employed as potent competitive inhibitors of glycosyltransferases. More particularly, uridine-5'-diphospho-2-deoxy-2-fluoro-galactose (UDP-2F-Gal), guanidine-5'-diphospho-2-deoxy-2-fluoro-L-fucose (GDP-2F-Fuc), uridine-51-diphospho-2-deoxy-2-fluoro-D-glucose (UDP-2F-Glu), guanosine-5'-diphospho-2-deoxy-2-fluoro-D-mannose (GDP-2F-Man), cytosine-5'-monophospho-2-deoxy-2-fluoro-D-sialic acid, and cytosine-5'-monophospho-2-deoxy-2-KDO may be employed as inhibitors of .beta.-1,4-galactosyltransferase, .alpha.-1,3-fucosyltransferase, glucosyltransferases, N-acetylglucosaminyltransferases, (.alpha.-mannosyltransferases, .alpha.-sialyltransferases, and KDO-transferases, respectively. Synthesis of nucleotide-linked-2-deoxy-2-fluoroglycosides is achieved using either chemoenzymatic or chemical methodologies.

  核苷酸连接的2-脱氧-2-氟糖苷被用作高效的糖基转移酶的竞争性抑制剂。特别是，尿苷-5'-二磷酸-2-脱氧-2-氟半乳糖（UDP-2F-Gal），鸟苷-5'-二磷酸-2-脱氧-2-氟-L-岩藻糖（GDP-2F-Fuc），尿苷-5'-二磷酸-2-脱氧-2-氟-D-葡萄糖（UDP-2F-Glu），鸟苷-5'-二磷酸-2-脱氧-2-氟-D-甘露糖（GDP-2F-Man），胞苷-5'-一磷酸-2-脱氧-2-氟-D-神经氨酸酸和胞苷-5'-一磷酸-2-脱氧-2-KDO可作为β-1,4-半乳糖基转移酶，α-1,3-岩藻糖基转移酶，葡萄糖基转移酶，N-乙酰葡萄糖胺基转移酶，（α-甘露糖基转移酶，α-神经氨酸酸基转移酶和KDO转移酶的抑制剂。核苷酸连接的2-脱氧-2-氟糖苷的合成可以通过化学酶法或化学方法实现。
• Addressing the Structural Complexity of Fluorinated Glucose Analogues: Insight into Lipophilicities and Solvation Effects
  作者：Jacob St‐Gelais、Émilie Côté、Danny Lainé、Paul A. Johnson、Denis Giguère

  DOI：10.1002/chem.202002825

  日期：2020.10.21

  glucopyranose analogues at positions C‐2, C‐3, C‐4, and C‐6. This systematic investigation allowed us to perform direct comparison of 19F resonances of fluorinated glucose analogues and also to determine their lipophilicities. Compounds with a fluorine atom at C‐6 are usually the most hydrophilic, whereas those with vicinal polyfluorinated motifs are the most lipophilic. Finally, the solvation energies

  在这项工作中，我们在位置C-2，C-3，C-4和C-6上合成了所有的单氟，双氟和三氟吡喃葡萄糖类似物。这项系统的研究使我们能够对氟化葡萄糖类似物的19 F共振进行直接比较，并确定它们的亲脂性。在C-6处带有氟原子的化合物通常是最亲水的，而具有邻位多氟基序的化合物则是最亲脂的。最后，使用密度泛函理论首次评估了氟化葡萄糖类似物的溶剂化能。此方法允许的日志 P氟葡萄糖类似物的预测，这是可比较的C日志 P从各种基于网络的方案获得的值。
• Sialidase substrate specificity studies using chemoenzymatically synthesized sialosides containing C5-modified sialic acids
  作者：Hongzhi Cao、Yanhong Li、Kam Lau、Saddam Muthana、Hai Yu、Jiansong Cheng、Harshal A. Chokhawala、Go Sugiarto、Lei Zhang、Xi Chen

  DOI：10.1039/b916305k

  日期：——

  para-Nitrophenol-tagged sialyl galactosides containing sialic acid derivatives in which the C5 hydroxyl group of sialic acids was systematically substituted with a hydrogen, a fluorine, a methoxyl or an azido group were successfully synthesized using an efficient chemoenzymatic approach. These compounds were used as valuable probes in high-throughput screening assays to study the importance of the C5 hydroxyl group of sialic acid in the recognition and the cleavage of sialoside substrates by bacterial sialidases.

  成功合成了标记有对硝基苯酚的含唾液酸衍生物的唾液酸半乳糖苷，这些衍生物中唾液酸的C5羟基以氢、氟、甲氧基或叠氮基进行了系统性的替代，采用了一种高效的化学酶法。这些化合物作为宝贵的探针，用于高通量筛选实验，研究了唾液酸C5羟基在细菌唾液酶识别和切割唾液苷底物中的重要性。
• Polyfluoroglycoside Synthesis via Simple Alkylation of an Anomeric Hydroxyl Group: Access to Fluoroetoposide Analogues
  作者：Thomas Tremblay、Jacob St-Gelais、Maxime Houde、Denis Giguère

  DOI：10.1021/acs.joc.0c02841

  日期：2021.3.19

  analogues. This strategy used a simple alkylation protocol and allowed the installation of a simple aglyconic alkane with the β configuration. Moreover, the glycosylation of fluorinated glucoside analogues with 4′-demethylepipodophyllotoxin furnished novel fluoroetoposide analogues. In these cases, the α anomers were formed as major products with an S configuration at the C-4 of the aglycone.

  在这项工作中，我们开发了一种合成氟糖苷类似物的新方法。该策略使用简单的烷基化方案，并允许安装具有β构型的简单无糖链烷烃。此外，氟化葡萄糖苷类似物与4'-脱甲基表鬼臼毒素的糖基化提供了新颖的氟依托泊苷类似物。在这些情况下，形成的α端基异构体是在糖苷配基的C-4处具有S构型的主要产物。
• Phosphodiesters serve as potentially tunable aglycones for fluoro sugar inactivators of retaining β-glycosidases
  作者：B. P. Rempel、S. G. Withers

  DOI：10.1039/c4ob00235k

  日期：——

  2-Deoxy-2-fluoroglycosides were synthesised and tested as covalent glycosidase inactivators. β-d-Gluco-, -manno- and -galacto-configured benzyl-benzylphosphonate derivatives efficiently inactivate β-gluco-, β-manno- and β-galactosidases, while α-gluco- and α-manno-configured phosphate and phosphonate derivatives instead served as slow substrates for their cognate α-glycosidases.

  2-脱氧-2-氟糖苷被合成并测试作为共价糖苷酶不活化剂。β-d-葡萄糖、-甘露糖和-半乳糖构型的苄基-苄基膦酸酯衍生物有效地不活化β-葡萄糖、β-甘露糖和β-半乳糖酶，而α-葡萄糖和α-甘露糖构型的磷酸盐和膦酸盐衍生物则作为其相应α-糖苷酶的缓慢底物。