methyl 3-deoxy-3-fluoro-β-D-glucopyranoside | 33941-75-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 3-deoxy-3-fluoro-β-D-glucopyranoside
• 英文别名: (2R,3R,4S,5S,6R)-4-fluoro-2-(hydroxymethyl)-6-methoxyoxane-3,5-diol
• CAS: 33941-75-2
• 化学式: C₇H₁₃FO₅
• 分子量: 196.176
• InChiKey: CCAXOPTXMDCKMO-IECVIRLLSA-N

物化性质

• 沸点：
  385.3±42.0 °C(Predicted)
• 密度：
  1.40±0.1 g/cm3(Predicted)

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：

  methyl 3-deoxy-3-fluoro-β-D-glucopyranoside 在 吡啶 、 咪唑 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 7.5h， 生成 methyl 6-O-(tert-butyldimethysilyl)-3-deoxy-2,4-di-O-trifluoromethanesulfonyl-3-fluoro-β-D-glucopyranoside
  参考文献：
  名称：

  3-Fluoroazetidinecarboxylic Acids and trans,trans-3,4-Difluoroproline as Peptide Scaffolds: Inhibition of Pancreatic Cancer Cell Growth by a Fluoroazetidine Iminosugar

  摘要：

  Reverse aldol opening tenders amides of 3-hydroxyazetidinecarboxylic acids (3-OH-Aze) unstable above pH 8. Axe, found in sugar beet, is mis-incorporated for proline in peptides in humans and is associated with multiple sclerosis and teratogenesis. Axe-containing peptides may be oxygenated by prolyl hydroxylases resulting in potential damage of the protein by a reverse aldol of the hydroxyazetidine; this, rather than changes in conformation; may account for the deleterious effects of Axe. This paper describes the synthesis of 3-fluoro-Aze amino acids as hydroxy-Aze analogues which are not susceptible to aldol cleavage. 4-(Azidomethyl)-3-fluoro-Aze and 3,4-difluoroproline are new peptide building blocks. trans,trans-2,4-dihydroxy-3-fluoroazetidine, an iminosugar, inhibits the growth of pancreatic cancer cells to a similar degree as gemcitabine.

  DOI：

  10.1021/acs.joc.5b00463
• 作为产物：
  描述：

  methyl 2,4,6-tri-O-acetyl-3-deoxy-3-fluoro-β-D-glucopyranoside 在 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 5.0h， 以96%的产率得到methyl 3-deoxy-3-fluoro-β-D-glucopyranoside
  参考文献：
  名称：

  3-Fluoroazetidinecarboxylic Acids and trans,trans-3,4-Difluoroproline as Peptide Scaffolds: Inhibition of Pancreatic Cancer Cell Growth by a Fluoroazetidine Iminosugar

  摘要：

  Reverse aldol opening tenders amides of 3-hydroxyazetidinecarboxylic acids (3-OH-Aze) unstable above pH 8. Axe, found in sugar beet, is mis-incorporated for proline in peptides in humans and is associated with multiple sclerosis and teratogenesis. Axe-containing peptides may be oxygenated by prolyl hydroxylases resulting in potential damage of the protein by a reverse aldol of the hydroxyazetidine; this, rather than changes in conformation; may account for the deleterious effects of Axe. This paper describes the synthesis of 3-fluoro-Aze amino acids as hydroxy-Aze analogues which are not susceptible to aldol cleavage. 4-(Azidomethyl)-3-fluoro-Aze and 3,4-difluoroproline are new peptide building blocks. trans,trans-2,4-dihydroxy-3-fluoroazetidine, an iminosugar, inhibits the growth of pancreatic cancer cells to a similar degree as gemcitabine.

  DOI：

  10.1021/acs.joc.5b00463

文献信息

• Cellulase-catalysed, stereoselective synthesis of oligosaccharides
  作者：Shin-Ichiro Shoda、Kei Obata、Olaf Karthaus、Shiro Kobayashi

  DOI：10.1039/c39930001402

  日期：——

  Oligosaccharides are synthesised enzymatically using β-lactosyl fluoride as glycosyl donor and a variety of mono-, di-and tri-saccharides as acceptors; the nature of the active site of the catalyst cellulase is discussed on the basis of these reactions.

  低聚糖通过酶法合成，以β-乳糖基氟化物为糖基供体，多种单糖、二糖和三糖作为受体；根据这些反应，探讨了催化剂纤维素酶活性中心的性质。
• 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。
• Synthesis of a novel fluorinated phosphonyl C-glycoside, (3-deoxy-3-fluoro-β-d-glucopyranosyl)methylphosphonate, a potential inhibitor of β-phosphoglucomutase
  作者：Madison Carroll-Poehls、David L. Jakeman

  DOI：10.1016/j.carres.2023.108979

  日期：2023.12

  Herein, the synthesis of a novel fluorinated phosphonyl C-glycoside (3-deoxy-3-fluoro-β-d-glucopyranosyl)methylphosphonate (1), in 12 steps (0.85 % overall yield) is disclosed. A four-stage synthetic strategy was employed, involving: 1) fluorine addition to the monosaccharide, 2) selective anomeric deprotection, 3) phosphonylation of the anomeric centre, and 4) global deprotection. Analysis of βPGM and 1

  β-磷酸葡萄糖变位酶 (βPGM) 通过两步过程催化 β-葡萄糖 1-磷酸 (βG1P) 转化为葡萄糖-6-磷酸 (G6P)，这是细胞能量的通用来源。由底物类似物和金属氟化物（MgF 3 -和 AlF 4 - ）形成的过渡态类似物（TSA）复合物能够独立分析每个酶促步骤。含有氟的新型底物类似物提供了使用19 F NMR 光谱来探究酶机制的机会。本文公开了新型氟化膦酰基C-糖苷(3-脱氧-3-氟-β- d-吡喃葡萄糖基)甲基膦酸酯( 1 )的合成，分12步进行(总收率0.85％)。采用四阶段合成策略，包括：1）向单糖添加氟，2）选择性异头去保护，3）异头中心磷酸化，以及4）整体去保护。 βPGM 和1的分析将在适当的时候报告。
• Karthaus, Olaf; Shoda, Shin-ichiro; Takano, Hiroshi, Journal of the Chemical Society. Perkin transactions I, 1994, # 13, p. 1851 - 1858
  作者：Karthaus, Olaf、Shoda, Shin-ichiro、Takano, Hiroshi、Obata, Kei、Kobayashi, Shiro

  DOI：——

  日期：——
• 3-Fluoroazetidinecarboxylic Acids and <i>trans,trans-</i>3,4-Difluoroproline as Peptide Scaffolds: Inhibition of Pancreatic Cancer Cell Growth by a Fluoroazetidine Iminosugar
  作者：Zilei Liu、Sarah F. Jenkinson、Tom Vermaas、Isao Adachi、Mark R. Wormald、Yukako Hata、Yukiko Kurashima、Akira Kaji、Chu-Yi Yu、Atsushi Kato、George W. J. Fleet

  DOI：10.1021/acs.joc.5b00463

  日期：2015.5.1

  Reverse aldol opening tenders amides of 3-hydroxyazetidinecarboxylic acids (3-OH-Aze) unstable above pH 8. Axe, found in sugar beet, is mis-incorporated for proline in peptides in humans and is associated with multiple sclerosis and teratogenesis. Axe-containing peptides may be oxygenated by prolyl hydroxylases resulting in potential damage of the protein by a reverse aldol of the hydroxyazetidine; this, rather than changes in conformation; may account for the deleterious effects of Axe. This paper describes the synthesis of 3-fluoro-Aze amino acids as hydroxy-Aze analogues which are not susceptible to aldol cleavage. 4-(Azidomethyl)-3-fluoro-Aze and 3,4-difluoroproline are new peptide building blocks. trans,trans-2,4-dihydroxy-3-fluoroazetidine, an iminosugar, inhibits the growth of pancreatic cancer cells to a similar degree as gemcitabine.