甲基 2-脱氧-2-氟-beta-D-吡喃葡萄糖苷 | 39110-58-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 甲基 2-脱氧-2-氟-beta-D-吡喃葡萄糖苷
• 中文别名: 甲基2-脱氧-2-氟-beta-D-吡喃葡萄糖苷
• 英文名称: methyl 2-deoxy-2-fluoro-β-D-glucopyranoside
• 英文别名: Methyl 2-deoxy-2-fluoro-b-D-glucopyranoside；(2R,3S,4S,5R,6R)-5-fluoro-2-(hydroxymethyl)-6-methoxyoxane-3,4-diol
• CAS: 39110-58-2
• 化学式: C₇H₁₃FO₅
• 分子量: 196.176
• InChiKey: CRIUOMMBWCCBCQ-NYMZXIIRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  79.2
• 氢给体数：
  3
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  甲基 2-脱氧-2-氟-beta-D-吡喃葡萄糖苷 在 palladium oxide on barium sulfate 4-二甲氨基吡啶 、 N-溴代丁二酰亚胺(NBS) 、 sodium azide 、 氢气 、 sodium methylate 、 silver fluoride 、 对甲苯磺酸 、 barium carbonate 作用下， 以 吡啶 、 甲醇 、 四氯化碳 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 29.33h， 生成 methyl 3-amino-2,3,6-trideoxy-2-fluoro-β-D-allopyranoside
  参考文献：
  名称：

  Synthesis of 3-amino-2,3,6-trideoxy-2-fluoro-l-talose and -d-allose [(R)-2-fluoro-l-daunosamine and (R)-2-fluoro-d-ristosamine]

  摘要：

  The title compounds were synthesized (as methyl glycosides) starting from 1,3,4,6-tetra-O-acetyl-2-deoxy-2-fluoro-beta-D-glucopyranose. Stereoselective methods of glycosylation gave, via the tri-O-acetylglycopyranosyl bromide, the methyl 2-deoxy-2-fluoro-alpha- and -beta-D-glucopyranoside triacetates. Each anomer was O-deacetylated and further transformed into the corresponding, 4,6-O-benzylidenated 3-triflate, and the triflates were converted by azide displacement into the 3-azido-2,3-dideoxy-2-fluoroglycosides having the D-allo configuration. Hanesssian-Hullar reaction then furnished the corresponding 6-bromo-6-deoxy-4-benzoates, which were dehydrobrominated to give the methyl 3-azido-4-O-benzoyl-2,3,6-tri-deoxy-2-fluoro-alpha- and -beta-D-ribo-hex-5-enopyranosides. Debenzoylation of the alpha-anomer, followed by catalytic hydrogenation, led to methyl 3-amino-2,3,6-trideoxy-2-fluoro-beta-L-talopyranoside [methyl (R)-2-fluoro-beta-L-daunosaminide], whereas the same sequence applied to the beta-anomer afforded methyl 3-amino-2,3,6-trideoxy-2-fluoro-beta-D-allopyranoside [methyl (R)-2-fluoro-beta-D-ristosaminide]. The overall yields for these 10-step sequences were 11-12 and 16%, respectively. The 1H- and 13C-n.m.r. data for the new fluoro sugar derivatives are discussed with respect to the dependence of JF,H and JF,C values on molecular geometry and substituent effects.

  DOI：

  10.1016/0008-6215(90)84168-t
• 作为产物：
  描述：

  methyl 3,4,6-tri-O-acetyl-2-deoxy-2-fluoro-β-D-glucopyranoside 在 sodium methylate 作用下， 以98%的产率得到甲基 2-脱氧-2-氟-beta-D-吡喃葡萄糖苷
  参考文献：
  名称：

  Synthesis of 3-amino-2,3,6-trideoxy-2-fluoro-l-talose and -d-allose [(R)-2-fluoro-l-daunosamine and (R)-2-fluoro-d-ristosamine]

  摘要：

  The title compounds were synthesized (as methyl glycosides) starting from 1,3,4,6-tetra-O-acetyl-2-deoxy-2-fluoro-beta-D-glucopyranose. Stereoselective methods of glycosylation gave, via the tri-O-acetylglycopyranosyl bromide, the methyl 2-deoxy-2-fluoro-alpha- and -beta-D-glucopyranoside triacetates. Each anomer was O-deacetylated and further transformed into the corresponding, 4,6-O-benzylidenated 3-triflate, and the triflates were converted by azide displacement into the 3-azido-2,3-dideoxy-2-fluoroglycosides having the D-allo configuration. Hanesssian-Hullar reaction then furnished the corresponding 6-bromo-6-deoxy-4-benzoates, which were dehydrobrominated to give the methyl 3-azido-4-O-benzoyl-2,3,6-tri-deoxy-2-fluoro-alpha- and -beta-D-ribo-hex-5-enopyranosides. Debenzoylation of the alpha-anomer, followed by catalytic hydrogenation, led to methyl 3-amino-2,3,6-trideoxy-2-fluoro-beta-L-talopyranoside [methyl (R)-2-fluoro-beta-L-daunosaminide], whereas the same sequence applied to the beta-anomer afforded methyl 3-amino-2,3,6-trideoxy-2-fluoro-beta-D-allopyranoside [methyl (R)-2-fluoro-beta-D-ristosaminide]. The overall yields for these 10-step sequences were 11-12 and 16%, respectively. The 1H- and 13C-n.m.r. data for the new fluoro sugar derivatives are discussed with respect to the dependence of JF,H and JF,C values on molecular geometry and substituent effects.

  DOI：

  10.1016/0008-6215(90)84168-t

文献信息

• 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。
• Improved synthesis of 2-deoxy-2-fluoro-D-glucose using fluoride ion.
  作者：TERUSHI HARADAHIRA、MINORU MAEDA、YASUNOBU KAI、HIROKO OMAE、MASAHARU KOJIMA

  DOI：10.1248/cpb.33.165

  日期：——

  Methyl 3-O-benzyl-4, 6-O-benzylidene-2-O-(trifluoromethanesulfonyl)-β-D-mannopyranoside (7) was examined as a substrate for the preparation of 2-deoxy-2-fluoro-D-glucose (1) by fluoride ion treatment. The triflate (7) reacted rapidly with tetraalkylammonium fluorides in acetonitrile or tetrahydrofuran to give methyl 3-O-benzyl-4, 6-O-benzylidene-2-deoxy-2-fluoro-β-D-glucopyranoside (10) in 52-57% yield. Removal of the protecting groups from 10 by the use of 50% methanesulfonic acid afforded the required 1 in good yield. This synthetic sequence may provide an effective alternative to known methods for preparing 18F-labeled 1.

  研究人员将 3-O-苄基-4，6-O-亚苄基-2-O-(三氟甲磺酰基)-β-D-吡喃甘露糖苷（7）作为底物，通过氟离子处理制备 2-脱氧-2-氟-D-葡萄糖（1）。三酸酯（7）与四烷基氟化铵在乙腈或四氢呋喃中迅速反应，得到甲基 3-O-苄基-4，6-O-亚苄基-2-脱氧-2-氟-β-D-吡喃葡萄糖苷（10），收率为 52-57%。用 50%的甲磺酸去除 10 中的保护基团，可以得到所需的 1，收率很高。这种合成方法可以有效替代已知的 18F 标记 1 的制备方法。
• BAER, HANS H.;HERNANDEZ, MATEO FERNANDO;SIEMSEN, LISA, CARBOHYDR. RES., 195,(1990) N, C. 225-245
  作者：BAER, HANS H.、HERNANDEZ, MATEO FERNANDO、SIEMSEN, LISA

  DOI：——

  日期：——
• Synthesis of 3-amino-2,3,6-trideoxy-2-fluoro-l-talose and -d-allose [(R)-2-fluoro-l-daunosamine and (R)-2-fluoro-d-ristosamine]
  作者：Hans.H. Baer、Fernando Hernández Mateo、Lisa Siemsen

  DOI：10.1016/0008-6215(90)84168-t

  日期：1990.1

  The title compounds were synthesized (as methyl glycosides) starting from 1,3,4,6-tetra-O-acetyl-2-deoxy-2-fluoro-beta-D-glucopyranose. Stereoselective methods of glycosylation gave, via the tri-O-acetylglycopyranosyl bromide, the methyl 2-deoxy-2-fluoro-alpha- and -beta-D-glucopyranoside triacetates. Each anomer was O-deacetylated and further transformed into the corresponding, 4,6-O-benzylidenated 3-triflate, and the triflates were converted by azide displacement into the 3-azido-2,3-dideoxy-2-fluoroglycosides having the D-allo configuration. Hanesssian-Hullar reaction then furnished the corresponding 6-bromo-6-deoxy-4-benzoates, which were dehydrobrominated to give the methyl 3-azido-4-O-benzoyl-2,3,6-tri-deoxy-2-fluoro-alpha- and -beta-D-ribo-hex-5-enopyranosides. Debenzoylation of the alpha-anomer, followed by catalytic hydrogenation, led to methyl 3-amino-2,3,6-trideoxy-2-fluoro-beta-L-talopyranoside [methyl (R)-2-fluoro-beta-L-daunosaminide], whereas the same sequence applied to the beta-anomer afforded methyl 3-amino-2,3,6-trideoxy-2-fluoro-beta-D-allopyranoside [methyl (R)-2-fluoro-beta-D-ristosaminide]. The overall yields for these 10-step sequences were 11-12 and 16%, respectively. The 1H- and 13C-n.m.r. data for the new fluoro sugar derivatives are discussed with respect to the dependence of JF,H and JF,C values on molecular geometry and substituent effects.