6-氟-6-脱氧-d-吡喃葡萄糖 | 34168-77-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 6-氟-6-脱氧-d-吡喃葡萄糖
• 中文别名: 6-脱氧-6-氟-D-葡萄糖
• 英文名称: 6-deoxy-6-fluoro-D-glucose
• 英文别名: 6-Fluoro-6-deoxy-d-glucopyranose；(3R,4S,5S,6S)-6-(fluoromethyl)oxane-2,3,4,5-tetrol
• CAS: 34168-77-9
• 化学式: C₆H₁₁FO₅
• 分子量: 182.149
• InChiKey: SHFYXYMHVMDNPY-GASJEMHNSA-N

物化性质

• 熔点：
  133-138
• 沸点：
  354.6±42.0 °C(Predicted)
• 密度：
  1.626±0.06 g/cm3(Predicted)
• 溶解度：
  甲醇（微溶）、水（微溶）

计算性质

• 辛醇/水分配系数(LogP)：
  -2.1
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  90.2
• 氢给体数：
  4
• 氢受体数：
  6

安全信息

• 安全说明：
  S22,S36/37/39
• 危险类别码：
  R20/21/22
• 海关编码：
  2932999099
• 储存条件：
  2-8°C

反应信息

• 作为反应物：
  描述：

  6-氟-6-脱氧-d-吡喃葡萄糖 在 aldose reductase 、 还原型辅酶II(NADPH)四钠盐 作用下， 以 水 为溶剂， 生成 6-fluoro-D-glucitol
  参考文献：
  名称：

  The use of fluoro- and deoxy-substrate analogs to examine binding specificity and catalysis in the enzymes of the sorbitol pathway

  摘要：

  The carbohydrate specificity of the two enzymes that catalyze the metabolic interconversions in the sorbitol pathway, aldose reductase and sorbitol dehydrogenase, has been examined through the use of fluoro- and deoxy-substrate analogs. Hydrogen bonding has been shown to be the primary mode of interaction by which these enzymes specifically recognize and bind their respective polyol substrates. Aldose reductase has broad substrate specificity, and all of the fluoro- and deoxysugars that were examined are substrates for this enzyme. Unexpectedly, both 3-fluoro- and 4-fluoro-D-glucose were found to be better substrates, with significantly lower K-m and higher k(cat)/K-m values than those of D-glucose. A more discriminating pattern of substrate specificity is observed for sorbitol dehydrogenase. Neither the 2-fluoro nor the 2-deoxy analogs of D-glucitol were found to be substrates or inhibitors, suggesting that the 2-hydroxyl group of sorbitol is a hydrogen bond donor. The 4-fluoro and 4-deoxy analogs are poorer substrates than sorbitol, also implying a binding role for this hydroxyl group. In contrast, both 6-fluoro- and 6-deoxy-D-glucitol are very good substrates for sorbitol dehydrogenase, indicating that the primary hydroxyl group at this position is not involved in substrate recognition by this enzyme. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(98)00266-3
• 作为产物：
  描述：

  6-deoxy-6-fluoro-α-D-glucopyranosyl [bis(cyclohexylammonium) phosphate] 在 高氯酸 作用下， 生成 6-氟-6-脱氧-d-吡喃葡萄糖
  参考文献：
  名称：

  一系列脱氧氟-d-吡喃葡萄糖基磷酸酯的合成与水解

  摘要：

  摘要描述了全部四种脱氧氟-α-d-吡喃葡萄糖基磷酸酯的合成。确定了其酸催化水解的速率常数，并且显示出氟取代在降低速率方面具有显著作用，特别是当取代邻近异头中心时。在25℃下在m HClO 4中测量的相对速率常数对于α-d-吡喃葡萄糖基磷酸酯和2-，3-，4-和6-脱氧氟衍生物分别为60.30：1.00：7.05：3.97：16.5。详细研究了2-脱氧-2-氟-α-d-吡喃葡萄糖基磷酸酯的水解，确定了4.1 eu（m反应物）和113.5 kJ.mol -1的活化熵和焓。在60°m HClO 4中的溶液中，研究了其水解的pH依赖性，并测定了单阴离子水解的速率常数（k M = 1。因此，提取了88×10 -6 s -1）和中性（k N = 6.23×10 -5 s -1）的物种。如所预期的，单阴离子的水解不受氟取代的显着影响。根据这些发现，合理化了几种机械上不同的酶利用这些氟化底物的能力或无能为力。

  DOI：

  10.1016/s0008-6215(00)90028-4

文献信息

• Enzymic aldol condensation/isomerization as a route to unusual sugar derivatives
  作者：J. Robert. Durrwachter、Dale G. Drueckhammer、Kenji. Nozaki、H. Marcel. Sweers、Chi Huey. Wong

  DOI：10.1021/ja00284a053

  日期：1986.11

  probes,* and chemical intermediate^.^ A recent review article reflects the importance of these compounds by enumerating hundreds of individual papers in the area of carbohydrate synthesis4 Traditional sources of rare or unnatural sugars have been chemical modification of natural sugars and total synthesis. The former was proven successful in many cases. However, total synthesis has evolved to a very

  已经开发了使用果糖二磷酸醛缩酶和葡萄糖异构酶作为催化剂的几种不寻常的己酮糖和己醛糖衍生物的制备性酶促合成。果糖二磷酸醛缩酶催化二羟基丙酮磷酸酯与许多醛之间的立体特异性醛醇缩合反应形成酮糖 1-磷酸，通过水解去除磷酸基团后，该酮糖在葡萄糖异构酶的催化下立体特异性地转化为醛糖衍生物。这些组合的酶促过程允许以 4-20 mmol 的规模制备 5-脱氧、6-脱氧、6-脱氧-6-氟-和 6-0-甲基己酮糖和 -己醛糖。已发现在无机砷酸盐存在下的二羟基丙酮是果糖二磷酸醛缩酶的有效底物。糖是一类无处不在的化合物，在生物化学中发挥着广泛的作用。因此，他们发现了作为药物、生物探针、* 和化学中间体^的应用。^ 最近的一篇评论文章通过列举碳水化合物合成领域的数百篇论文4 反映了这些化合物的重要性4 稀有或非天然糖的传统来源已对天然糖类进行化学修饰和全合成。前者在许多情况下被证明是成功的。然而，全合成已经发展到
• [EN] NEOGLYCORANDOMIZATION AND DIGITOXIN ANALOGS<br/>[FR] ALEATOIRISATION DES NEOGLYCOSIDES ET ANALOGUES DE LA DIGITOXINE
  申请人：WISCONSIN ALUMNI RES FOUND

  公开号：WO2006002381A1

  公开（公告）日：2006-01-05

  The present invention provides methods of producing libraries of compounds with enhanced desirable properties and diminished side effects as well as the compounds produced by the methods. In preferred embodiments, methods of the present invention use a universal chemical glycosylation method that employs reducing sugars and requires no protection or activation. In a preferred embodiment, the invention provides a library of neoglycoside digitoxin analogs that includes compounds with significantly enhanced cytotoxic potency toward human cancer cells and tumor-specificity, but are less potent Na+/K+-ATPase inhibitors in a human cell line than digitoxin.

  本发明提供了一种生产具有增强理想性能和减少副作用的化合物库的方法，以及通过这些方法生产的化合物。在优选实施例中，本发明的方法使用一种通用的化学糖基化方法，该方法采用还原糖，无需保护或激活。在优选实施例中，本发明提供了一种新糖苷地高辛类似物库，其中包括对人类癌细胞具有显著增强的细胞毒性活性和肿瘤特异性的化合物，但在人类细胞系中对Na+/K+-ATPase的抑制作用较地高辛要弱。
• Chemoenzymatic Synthesis of Fluorinated Cellodextrins Identifies a New Allomorph for Cellulose‐Like Materials**
  作者：Peterson Andrade、Juan C. Muñoz‐García、Giulia Pergolizzi、Valeria Gabrielli、Sergey A. Nepogodiev、Dinu Iuga、László Fábián、Rinat Nigmatullin、Marcus A. Johns、Robert Harniman、Stephen J. Eichhorn、Jesús Angulo、Yaroslav Z. Khimyak、Robert A. Field

  DOI：10.1002/chem.202003604

  日期：2021.1.18

  the self‐assembly of building blocks into complex hierarchical structures represents a major challenge en route to the design and preparation of soft‐matter materials with specific properties. Enzymatically synthesised cellodextrins are known to have limited water solubility beyond DP9, a point at which they self‐assemble into particles resembling the antiparallel cellulose II crystalline packing. We

  了解构建块自组装成复杂分层结构的细节是设计和制备具有特定性能的软物质材料的主要挑战。已知酶法合成的纤维糊精在 DP9 之外具有有限的水溶性，此时它们会自组装成类似于反平行纤维素 II 晶体堆积的颗粒。我们通过化学酶法合成制备并表征了一系列具有不同氟化程度和取代模式的位点选择性氟化纤维糊精。考虑到纤维素 II 氢键网络的潜在破坏，我们制备并表征了多重 6-氟化纤维糊精。此外，还合成了一系列单位点选择性氟化纤维糊精，以评估每条链添加一个氟原子对结构的影响。结合先进的核磁共振波谱和显微镜方法，对这些材料在不同长度尺度上的结构表征表明，6-氟化供体基质产生了多个6-氟化纤维糊精链，这些链组装成具有形态和结晶特征以及分子间相互作用的颗粒，这对于类纤维素材料来说是前所未有的。
• Anomeric Selectivity of Trehalose Transferase with Rare <scp>l</scp>-Sugars
  作者：Luuk Mestrom、Stefan R. Marsden、Hessel van der Eijk、Jesper U. Laustsen、Cy M. Jeffries、Dmitri I. Svergun、Peter-Leon Hagedoorn、Isabel Bento、Ulf Hanefeld

  DOI：10.1021/acscatal.0c02117

  日期：2020.8.7

  glycosyltransferases catalyze the formation of glycosidic bonds between nucleotide sugar donors and carbohydrate acceptors. The anomeric selectivity of trehalose transferase from Thermoproteus uzoniensis was investigated for both d- and l-glycopyranose acceptors. The enzyme couples a wide range of carbohydrates, yielding trehalose analogues with conversion and enantioselectivity of >98%. The anomeric selectivity inverts

  保留LeLoir糖基转移酶可催化核苷酸糖供体和碳水化合物受体之间糖苷键的形成。研究了对于d-和l- glycopyranose受体，来自uzoniensis的Thermoproteus uzoniensis的海藻糖转移酶的异头选择性。该酶偶联多种碳水化合物，产生海藻糖类似物，其转化率和对映选择性> 98％。从α异头选择性反转，α-（1→1） -糖苷键d -glycopyranose受体到α，β-（1→1） -糖苷键为升-glycopyranose受体，而（小号两种糖受体的选择性都保留下来。比较海藻糖转移酶与α，α-海藻糖和非天然α，β-海藻糖类似物的蛋白质晶体结构，突出了观察到的异头选择性逆转的机理。
• Chemoenzymatic Synthesis of Trehalose Analogues: Rapid Access to Chemical Probes for Investigating Mycobacteria
  作者：Bailey L. Urbanek、Douglas C. Wing、Krystal S. Haislop、Chelsey J. Hamel、Rainer Kalscheuer、Peter J. Woodruff、Benjamin M. Swarts

  DOI：10.1002/cbic.201402288

  日期：2014.9.22

  Trehalose tools for TB: A one‐step chemoenzymatic method for the rapid and efficient synthesis of trehalose analogues was developed. This method enabled facile preparation and administration of a trehalose‐based probe for detecting mycobacteria, which might enable the development of new diagnostic tools for tuberculosis (TB) research.

  用于结核病的海藻糖工具：开发了一种用于快速有效合成海藻糖类似物的一步化学酶法。这种方法使得可以方便地制备和使用基于海藻糖的探针来检测分枝杆菌，这可能有助于开发用于结核病（TB）研究的新诊断工具。