methyl 3,4,6-tri-O-acetyl-2-deoxy-2-fluoro-α-D-glucopyranoside | 115216-39-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: methyl 3,4,6-tri-O-acetyl-2-deoxy-2-fluoro-α-D-glucopyranoside
• 英文别名: [(2R,3R,4S,5R,6S)-3,4-diacetyloxy-5-fluoro-6-methoxyoxan-2-yl]methyl acetate
• CAS: 115216-39-2
• 化学式: C₁₃H₁₉FO₈
• 分子量: 322.287
• InChiKey: XSRMZIRCCCSJNW-VEGXAWMVSA-N

物化性质

• 熔点：
  80-81 °C(Solv: ethyl ether (60-29-7); hexane (110-54-3))
• 沸点：
  375.0±42.0 °C(Predicted)
• 密度：
  1.26±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  22
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  97.4
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  methyl 3,4,6-tri-O-acetyl-2-deoxy-2-fluoro-α-D-glucopyranoside 在 吡啶 、 叠氮化锂 、 sodium methylate 、 对甲苯磺酸 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 15.25h， 生成 methyl 4,6-O-benzylidene-2,3-dideoxy-2-fluoro-α-D-erythro-hex-2-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
• 作为产物：
  描述：

  1,3,4,6-tetra-O-acetyl-2-deoxy-2-fluoro-β-D-glucopyranose 在 四丁基溴化铵 、 氢溴酸 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 、 氯仿 、 溶剂黄146 为溶剂， 反应 51.0h， 生成 methyl 3,4,6-tri-O-acetyl-2-deoxy-2-fluoro-α-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

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：——
• MODIFIED KOJIBIOSIDES ANALOGUES
  申请人：ALBERTA RESEARCH COUNCIL

  公开号：EP0830365A1

  公开（公告）日：1998-03-25
• US5633233A
  申请人：——

  公开号：US5633233A

  公开（公告）日：1997-05-27
• US5877157A
  申请人：——

  公开号：US5877157A

  公开（公告）日：1999-03-02
• [EN] MODIFIED KOJIBIOSIDES ANALOGUES<br/>[FR] ANALOGUES KOJIBIOSIDES MODIFIES
  申请人：ALBERTA RESEARCH COUNCIL

  公开号：WO1996040702A1

  公开（公告）日：1996-12-19

  (EN) Disclosed are novel analogues of kojibiose and pharmaceutical compositions comprising such analogues.(FR) L'invention concerne de nouveaux analogues de kojibiose et des compositions pharmaceutiques comprenant de tels analogues.