methyl 4,6-O-benzylidene-2-deoxy-2-fluoro-3-O-(trifluoromethylsulfonyl)-β-D-glucopyranoside | 128854-96-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: methyl 4,6-O-benzylidene-2-deoxy-2-fluoro-3-O-(trifluoromethylsulfonyl)-β-D-glucopyranoside
• CAS: 128854-96-6
• 化学式: C₁₅H₁₆F₄O₇S
• 分子量: 416.347
• InChiKey: NVYKCKMSPQSTQK-FAYOZSNISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.04
• 重原子数：
  27.0
• 可旋转键数：
  4.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  80.29
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  methyl 4,6-O-benzylidene-2-deoxy-2-fluoro-3-O-(trifluoromethylsulfonyl)-β-D-glucopyranoside 在 N-溴代丁二酰亚胺(NBS) 、 sodium azide 、 barium carbonate 作用下， 以 四氯化碳 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.33h， 生成 methyl 3-azido-4-O-benzoyl-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 、 对甲苯磺酸 作用下， 以 吡啶 、 二氯甲烷 、 乙腈 为溶剂， 生成 methyl 4,6-O-benzylidene-2-deoxy-2-fluoro-3-O-(trifluoromethylsulfonyl)-β-D-glucopyranoside
  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