methyl 3-azido-2,3,6-trideoxy-2-fluoro-α-D-ribo-hex-5-enopyranoside | 128854-94-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: methyl 3-azido-2,3,6-trideoxy-2-fluoro-α-D-ribo-hex-5-enopyranoside
• 英文别名: (3S,4R,5R,6S)-4-azido-5-fluoro-6-methoxy-2-methylideneoxan-3-ol
• CAS: 128854-94-4
• 化学式: C₇H₁₀FN₃O₃
• 分子量: 203.173
• InChiKey: JFCYUMMZCDMOKU-UCROKIRRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.88
• 重原子数：
  14.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  87.45
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  methyl 3-azido-2,3,6-trideoxy-2-fluoro-α-D-ribo-hex-5-enopyranoside 在 palladium oxide on barium sulfate 氢气 作用下， 以 甲醇 为溶剂， 反应 4.0h， 以58%的产率得到Methyl 3-amino-2,3,6-trideoxy-2-fluoro-β-L-talopyranoside
  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 2-deoxy-2-fluoro-α-D-glucopyranoside 在 吡啶 、 N-溴代丁二酰亚胺(NBS) 、 叠氮化锂 、 sodium methylate 、 对甲苯磺酸 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 barium carbonate 作用下， 以 甲醇 、 四氯化碳 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 乙腈 、 苯 为溶剂， 反应 22.42h， 生成 methyl 3-azido-2,3,6-trideoxy-2-fluoro-α-D-ribo-hex-5-enopyranoside
  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

• 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：——