6-deoxy-6-fluorogalactose

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6-deoxy-6-fluorogalactose
• 英文别名: 6-deoxy-6-fluoro-D-galactose；6-deoxy-6-fluoro-D-galactopyranose；(3R,4S,5R,6S)-6-(fluoromethyl)tetrahydropyran-2,3,4,5-tetrol；Gal6F；6-Fluoro-6-deoxy-D-galactopyranose；(3R,4S,5R,6S)-6-(fluoromethyl)oxane-2,3,4,5-tetrol
• 化学式: C₆H₁₁FO₅
• 分子量: 182.149
• InChiKey: SHFYXYMHVMDNPY-SVZMEOIVSA-N

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

反应信息

• 作为反应物：
  描述：

  6-deoxy-6-fluorogalactose 在 bacterial galactokinase (LgGalK) cloned from Leminorella grimontii 、 5’-三磷酸腺苷 、 magnesium chloride 作用下， 以 aq. buffer 为溶剂， 反应 2.0h， 生成
  参考文献：
  名称：

  具有化学活性的6-氨基半乳糖-1-磷酸盐及其类似物化学合成的高活性细菌半乳糖激酶的表征

  摘要：

  提供磷酸盐：已经鉴定并鉴定了来自格氏乳杆菌的半乳糖激酶（LgGalK）；它对不同的核苷酸磷酸和单糖显示出广泛的底物特异性。该酶与半乳糖氧化酶变体结合在一起，用于化学酶合成6-氨基半乳糖-1-磷酸类似物。

  DOI：

  10.1002/cbic.201700477
• 作为产物：
  描述：

  Α-D-乳酸吡喃糖苷甲酯 在 二乙胺基三氟化硫 、 水 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 8.5h， 生成 6-deoxy-6-fluorogalactose
  参考文献：
  名称：

  UDP-6-deoxy-6-fluoro-α-d-galactose binds to two different galactosyltransferases, but neither can effectively catalyze transfer of the modified galactose to the appropriate acceptor

  摘要：

  The effect of substitution of the HO-6 of D-galactose with fluorine on the ability of alpha-(1 --> 3)-galactosyltransferase (EC 2.4.1.151) and beta-(1 --> 4)-galactosyltransferase (EC 2.4.1.22) to catalyze its transfer from UDP to an appropriate acceptor was determined. HPLC analyses indicated that each transferase properly catalyzed formation of the expected product [beta-D-Gal-(1 --> 4)-D-GlcNAc for the beta-(1 --> 4)-galactosyltransferase and alpha-D-Gal-(1 --> 3)-beta-D-Gal-(1 --> 4)-D-GlcNAc for the alpha-(1 --> 3)-D-galactosyltransferase] when UDP-alpha-D-Gal was the substrate. When UDP-6-deoxy-6-fluoro-alpha-D-galactose (6) was used in conjunction with each transferase, no product indicative of transfer of 6-deoxy-6-fluoro-D-galactose to its respective acceptor sugar was identified. 6-Deoxy-6-fluoro-D-galactose (3) was obtained by hydrolysis of methyl 6-deoxy-6-fluoro-alpha-D-galactopyranoside, synthesized by the selective fluorination of methyl alpha-D-galactopyranoside with diethylaminosulfur trifluoride (DAST), with aqueous trifluoroacetic acid. Acetylation of 3 gave crystalline 1,2,3,4-tetra-O-acetyl-6-deoxy-6-fluoro-beta-D-galactopyranose, which was converted to the corresponding 1-alpha-phosphate and used for the synthesis of 6. (C) 1999 Published by Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(99)00104-4

文献信息

• 唾液酸化TF抗原及其氟代衍生物的合成方法 及其应用
  申请人：天津科技大学

  公开号：CN108164573B

  公开（公告）日：2020-08-04

  本发明公开了一种唾液酸化TF抗原及其氟代衍生物的合成方法及其应用，其包含下列步骤：⑴化学合成氟代半乳糖及氟代半乳糖胺类似物；⑵化学法合成氟代TF抗原；⑶酶法合成唾液酸化TF抗原及其氟代衍生物。本发明将化学合成法的灵活性和酶合成法的高区域选择性和高效性结合到一起，首次实现了氟代唾液酸化TF抗原的酶法合成，解决了目前化学合成氟代唾液酸化TF抗原中所面临的合成步骤繁多、立体选择性不高、收率低、使用重金属盐等缺点。由于氟代肿瘤相关糖抗原具有比天然糖抗原稳定性更高，因而，本发明在发展新型抗肿瘤疫苗具有广泛的应用前景。
• Recognition of synthetic deoxy and deoxyfluoro analogs of the acceptor α-l-Fucp-(1 → 2)-β-d-Galp-OR by the blood-group A and B gene-specified glycosyltransferases
  作者：Todd L. Lowary、Ole Hindsgaul

  DOI：10.1016/0008-6215(93)84068-h

  日期：1993.10

  Abstract The disaccharide α- l -Fuc p -O-(CH 2 ) 7 CH 3 (6) , is an acceptor for both glycosyltransferases responsible for the biosynthesis of the A and B blood-group antigens. These enzymes transfer GalNAc and Gal, respectively, with an α-linkage to OH-3 of the Gal residue in 6 . All six possible deoxy and deoxyfluoro analogs of 6 , with modifications on the target Gal residue, were chemically synthesized

  摘要二糖α-1-Fucp -O-（CH 2）7 CH 3（6）是负责A和B血型抗原生物合成的两个糖基转移酶的受体。这些酶分别将GalNAc和Gal转移至6中Gal残基的OH-3上，且具有α键。化学合成了6种在目标Gal残基上有修饰的6种可能的6种脱氧和脱氧氟类似物，并进行了动力学评估，作为A和B糖基转移酶的底物和抑制剂。两种酶都将耐受Gal残基的3和6位羟基的取代。但是，Gal残基的OH-4取代取代了这些糖基转移酶的识别。6脱氧和6氟化合物是这两种酶的底物，而3脱氧和3氟化合物是竞争性抑制剂，K i值在14–110μM范围内。已经确定了6-脱氧和6-氟衍生物的动力学常数。
• Fluorinated Glycosyl Amino Acids for Mucin-Like Glycopeptide Antigen Analogues
  作者：Sarah Wagner、Christian Mersch、Anja Hoffmann-Röder

  DOI：10.1002/chem.200903294

  日期：2010.6.25

  development of immunotherapy against cancer. Mucin‐type glycopeptides have been successfully investigated as molecularly defined vaccine prototypes for triggering humoral immunity but are susceptible to rapid in vivo degradation. As a potential means to enhance the bioavailabilities of the antigenic structures, hydrolysis‐resistant carbohydrate analogues with fluorine substituents at positions C6, C2′ and

  粘蛋白糖蛋白在上皮肿瘤细胞上的异常糖基化概况代表了针对癌症的免疫疗法发展的有吸引力的靶结构。粘蛋白型糖肽已作为分子定义的疫苗原型成功进行了研究，可触发体液免疫，但易于在体内迅速降解。作为增强抗原结构生物利用度的潜在手段，合成了在位置C6，C2'和C6'具有氟取代基的耐水解碳水化合物类似物，并将其掺入粘蛋白MUC1的串联重复序列中。由此产生的伪糖肽可用于阐明化学修饰的抗体决定簇对代谢和免疫学特性的影响。
• Efficient chemoenzymatic synthesis of novel galacto-N-biose derivatives and their sialylated forms
  作者：Lei Li、Yonghui Liu、Tiehai Li、Wenjun Wang、Zaikuan Yu、Cheng Ma、Jingyao Qu、Wei Zhao、Xi Chen、Peng G. Wang

  DOI：10.1039/c5cc03746h

  日期：——

  Novel galacto-N-biose derivatives and their sialylated form were efficiently synthesizedviaone-pot two-enzyme systems starting with monosaccharides.

  通过单糖开始，使用一锅两酶系统高效合成了新型半乳糖-N-生物素衍生物及其唾液酸化形式。

• Chemoenzymatic synthesis of mono- and di-fluorinated Thomsen–Friedenreich (T) antigens and their sialylated derivatives
  作者：Jun Yan、Xi Chen、Fengshan Wang、Hongzhi Cao

  DOI：10.1039/c2ob26989a

  日期：——

  Fluorinated Thomsen–Friedenreich (T) antigens were synthesized efficiently from chemically produced fluorinated monosaccharides using a highly efficient one-pot two-enzyme chemoenzymatic approach containing a galactokinase and a D-galactosyl-β1–3-N-acetyl-D-hexosamine phosphorylase. These fluorinated T-antigens were further sialylated to form fluorinated ST-antigens using a one-pot two-enzyme system

  氟化 Thomsen-Friedenreich (T) 抗原是使用含有半乳糖激酶和D-半乳糖基-β1-3- N-乙酰-D-己糖胺磷酸化酶的高效一锅双酶化学酶法从化学生产的氟化单糖有效合成的。使用含有 CMP-唾液酸合成酶和 α-2-3-唾液酸转移酶的一锅双酶系统将这些氟化 T 抗原进一步唾液酸化以形成氟化 ST 抗原。