1,3,4,6-tetra-O-acetyl-2-deoxy-2-fluoro-β-D-glucopyranose | 31077-89-1

• 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-fluoro-β-D-glucopyranose
• 英文别名: 1,3,4,6-tetra-O-acetyl-2-deoxy-2-fluoro-β-D-glucose；1,3,4,6-tetra-O-acetyl-2-deoxy-2-fluoro-D-glucopyranose；1,3,4,6-tetra-O-Acetyl-2-deoxy-2-fluoro-beta-D-glucopyranose；[(2R,3R,4S,5R,6S)-3,4,6-triacetyloxy-5-fluorooxan-2-yl]methyl acetate
• CAS: 31077-89-1
• 化学式: C₁₄H₁₉FO₉
• 分子量: 350.298
• InChiKey: KIPRSJXOVDEYLX-DHGKCCLASA-N

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-fluoro-β-D-glucopyranose 在 ammonium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 26.0h， 以100%的产率得到3,4,6-tri-O-acetyl-2-deoxy-2-fluoro-D-glucopyranose
  参考文献：
  名称：

  Substrate specificity of N-acetylglucosaminyl(diphosphodolichol) N-acetylglucosaminyl transferase, a key enzyme in the dolichol pathway

  摘要：

  N-Acetylglucosaminyl(diphosphodolichol) N-acetylglucosaminyl transferase, also known as Enzyme II, is the second enzyme in the dolichol pathway. This pathway is responsible for the assembly of the tetradecasaccharide pyrophosphate dolichol, which is the substrate for oligosaccharyl transferase. In order to study the specificity of Enzyme II, four unnatural dolichol diphosphate monosaccharides were synthesized, with the C-2 acetamido group in the natural substrate Dol-PP-GlcNAc la replaced by fluoro, ethoxy, trifluoroacetamido, and amino functionalities. These analogues Ib-e were evaluated as glycosyl accepters for Enzyme II, which catalyzes the formation of dolichol diphosphate chitobiose (Dol-PP-GlcNAc(2)) from UDP-GlcNAc and Dol-PP-GlcNAc. Enzyme II from pig liver was found to be highly specific for its glycosyl acceptor and the acetamido group shown to be a key functional determinant for this glycosylation reaction. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0968-0896(00)00334-5
• 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-fluoro-β-D-glucopyranose
  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

• Studies on the Reaction of D-Glucal and its Derivatives with 1-Chloromethyl-4-Fluoro-1,4-Diazoniabicyclo[2.2.2]Octane Salts
  作者：J. Ortner、M. Albert、H. Weber、K. Dax

  DOI：10.1080/07328309908543997

  日期：1999.1.1

  ABSTRACT The reaction of D-glucal and its derivatives with the electrophilic N-F-fluorination reagents F-TEDA tetrafluoroborate and triflate was studied by means of 19F NMR spectroscopy. In all cases mixtures of 2-deoxy-2-fluoro-D-gluco- and -D-mannopyranose derivatives were formed, the ratio of which was dependent on the nature of the O-protecting groups. Concerning the products arising from the direct

  摘要利用19F NMR光谱研究了D-葡萄糖及其衍生物与亲电NF-氟化试剂F-TEDA四氟硼酸酯和三氟甲磺酸酯的反应。在所有情况下，均形成2-脱氧-2-氟-D-葡萄糖-和-D-甘露吡喃糖衍生物的混合物，其比例取决于O-保护基团的性质。关于直接通过双键添加试剂产生的产物，D-葡萄糖构型的化合物（13-20）通常显示出比其D-甘露聚糖对应物（21-28）更高的水解速率。仅当形成单个端基异构体（例如2,4-二硝基苯基糖苷29e / 37e和二糖氟化物35d / 43d）或过氧乙酸酯（例如29f / 37f）时，才能实现产品分离。
• Chemoenzymatic n.c.a synthesis of the coenzyme UDP-2-deoxy-2-[18F]fluoro-α-D-glucopyranose as substrate of glycosyltransferases
  作者：Olaf Prante、Kurt Hamacher、Heinz H. Coenen

  DOI：10.1002/jlcr.1161

  日期：——

  glycosyltransferases. The MacDonald synthesis of [18F]FDG-1-phosphate was successfully combined with an enzymatic activation to obtain UDP-[18F]FDG directly in an aqueous medium located in the void volume of a solid phase cartridge. The radiochemical yield of UDP-[18F]FDG was 20% (based on [18F]fluoride) after a total synthesis time of 110 min. Thus, an intermediate was provided for the enzymatic transfer of [18F]FDG

  用于蛋白质和生物活性肽的 18F 标记方法的发展在放射性药物科学中引起了极大的兴趣。为了提供 18F 标记的糖作为酶促 18F 标记程序的极性辅基，需要适当的核苷酸活化糖。在这里，我们介绍了作为糖基转移酶底物的 nca UDP-2-deoxy-2-[18F] 氟-α-D-吡喃葡萄糖 (UDP-[18F]FDG) 的放射合成。[18F]FDG-1-磷酸盐的 MacDonald 合成成功地与酶促活化相结合，直接在位于固相柱空隙体积的水性介质中获得 UDP-[18F]FDG。在 110 分钟的总合成时间后，UDP-[18F]FDG 的放射化学产率为 20%（基于 [18F] 氟化物）。因此，使用UDP-[18F]FDG作为糖基供体，利用合适的糖基转移酶，提供了用于酶促转移[18F]FDG的中间体。这将代表一种用于糖基化生物分子的高选择性和温和的 18F 标记方法。版权所有 © 2007 John
• The synthesis and hydrolysis of a series of deoxyfluoro-d-glucopyranosyl phosphates
  作者：Stephen G. Withers、David J. MacLennan、Ian P. Street

  DOI：10.1016/s0008-6215(00)90028-4

  日期：1986.10

  for α- d -glucopyranosyl phosphate and the 2-, 3-, 4- and 6-deoxyfluoro derivatives, respectively. The hydrolysis of 2-deoxy-2-fluoro-α- d -glucopyranosyl phosphate was studied in more detail, and an activation entropy and enthalpy of 4.1 e.u. ( m reactant) and 113.5 kJ.mol −1 , respectively, were determined for hydrolysis in m HClO 4 at 60° The pH dependence of its hydrolysis was investigated, and rate

  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。
• Synthesis and N.M.R. spectra of methyl 2-deoxy-2-fluoro- and 3-deoxy-3-fluoro-α- and β-d-glucopyranosides
  作者：Pavol Kováč、Herman J.C. Yeh、Cornelis P.J. Glaudemans

  DOI：10.1016/0008-6215(87)80239-2

  日期：1987.11

  silver perchlorate-catalyzed glycosylation showed remarkable lack of stereoselectivity for the formation of the corresponding methyl alpha-glycoside, despite the presence at C-2 of the fluorine functionality presumably not capable of neighboring-group participation. Pure methyl 2-deoxy-2-fluoro-alpha- and beta-D-glucopyranosides were obtained by fractional crystallization from the mixture formed by methanolysis

  甲基3-脱氧-3-氟-α-和β-D-吡喃葡萄糖苷以及α-和β-D-葡糖呋喃糖苷是通过3-脱氧-3-氟-1,2：5,6-di-O的甲醇分解制得的-异亚丙基-α-D-葡萄糖呋喃糖。结晶3,4,6-三-O-乙酰基-2-脱氧-2-氟-α-D-吡喃葡萄糖基氯（2）和相应的糖基溴化物（3）由1,3,4,6-四甲基制得-O-乙酰基-2-脱氧-2-氟-β-D-吡喃葡萄糖（1）。在三氟甲磺酸银和高氯酸银催化的糖基化条件下，2与甲醇的反应表明，尽管在C-2处存在氟官能团可能无法分离，但对于形成相应的甲基α-糖苷而言，明显缺乏立体选择性。邻居参与。
• Conjugates of 2-fluoro-2-deoxy-glucose and their uses as anti cancer agents
  申请人：INSTITUT NATIONAL DE LA SANTE ET DE LA RECHERCHE MEDICALE (INSERM)

  公开号：EP1881000A1

  公开（公告）日：2008-01-23

  The present invention relates to compounds of general formula (I): wherein: - R1, R2 and R3 mean, independently from the others, an hydrogen atom or an optionally substituted lower alkyl, a (C1-C7)acyl group or a benzyl, - R4 is an optionally substituted and/or interrupted hydrocarbon linker, - X and Y are selected independently from each other from the group consisting of -NH-, -NR'-, -CO-, -NH(CO)-, -NH(CO)NH-, -NR'(CO)-, -O(CO)NH-, -O(CO)NR'-, -(CO)NH-, -(CO)NR'-, -NH(CO)(R")NH(CO)-, -(CO)NH(R"(CO)NH-, -O-, -(CO)O-, -NH(CO)O-, -SC(O)NH-, -NHSO2-, -NR'SO2- and -O(CO)- and preferably are different one from the other, with R' being an optionally substituted lower alkyl group, and R" being a (C1-C3) alkylene, - Z moiety represents an anti-neoplasic agent, - n means 0 or 1, - and the pharmaceutically acceptable salts thereof. It relates also to the use of such compounds as anti cancer agents.

  本发明涉及一般式（I）的化合物：其中：- R1、R2和R3分别独立地表示氢原子或可选择取代的较低烷基，（C1-C7）酰基团或苄基，- R4是可选择取代和/或中断的碳氢链，- X和Y分别独立地从-NH-，-NR'-，-CO-，-NH（CO）-，-NH（CO）NH-，-NR'（CO）-，-O（CO）NH-，-O（CO）NR'-，-（CO）NH-，-（CO）NR'-，-NH（CO）（R"）NH（CO）-，-（CO）NH（R"（CO）NH-，-O-，-（CO）O-，-NH（CO）O-，-SC（O）NH-，-NHSO2-，-NR'SO2-和-O（CO）-中选择，并且最好彼此不同，其中R'是可选择取代的较低烷基团，R"是（C1-C3）烷基，- Z基团代表抗肿瘤剂，- n表示0或1，- 及其药用盐。还涉及将这些化合物用作抗癌剂。