3,4,6-tri-O-acetyl-1,2-O-(exo-trifluoroethoxyethylidene)-α-D-glucopyranose | 211293-10-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: 3,4,6-tri-O-acetyl-1,2-O-(exo-trifluoroethoxyethylidene)-α-D-glucopyranose
• 英文别名: [(2S,3aR,5R,6R,7S,7aR)-6,7-diacetyloxy-2-methyl-2-(2,2,2-trifluoroethoxy)-5,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-b]pyran-5-yl]methyl acetate
• CAS: 211293-10-6
• 化学式: C₁₆H₂₁F₃O₁₀
• 分子量: 430.332
• InChiKey: BJAOYJAWUJVDTC-KYFQHEKYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  29
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  116
• 氢给体数：
  0
• 氢受体数：
  13

反应信息

• 作为反应物：
  描述：

  3,4,6-tri-O-acetyl-1,2-O-(exo-trifluoroethoxyethylidene)-α-D-glucopyranose 在 高氯酸四乙基铵 、 potassium hydride 、 (+)-10-camphorsulfonic acid 作用下， 以 四氢呋喃 、 1,2-二氯乙烷 为溶剂， 反应 5.0h， 生成 methyl 2-O-acetyl-3,4,6-tri-O-benzyl-β-D-glucopyranosyl-(1→4)-2,3,6-tri-O-benzyl-α-D-glucopyranoside
  参考文献：
  名称：

  Stereospecific Access to β-Mannosides from Glucose-derived 1,2-Orthoesters as Glycosyl Donors

  摘要：

  A new, stereospecific synthesis of beta-mannosides from glucose-derived 1,2-orthoesters has been developed by a simple four step procedure, comprising beta-specific glycosidation of the 1,2-orthoesters, 2'-O-deacetylation, 2'-O-triflation, and SN 2 type inversion of the triflyl group providing beta-D-Man-(1-->6)-D-Gal, and beta-D-Man-(1-->4)-D-Glc derivatives in reasonable yield.

  DOI：

  10.3987/com-03-s60
• 作为产物：
  描述：

  2,2,2-三氟乙醇 、 2,3,4,6-四乙酰氧基-alpha-D-吡喃葡萄糖溴化物 在 2,4,6-三甲基吡啶 、 四丁基溴化铵 作用下， 以 二氯甲烷 为溶剂， 反应 14.0h， 以75.2%的产率得到3,4,6-tri-O-acetyl-1,2-O-(exo-trifluoroethoxyethylidene)-α-D-glucopyranose
  参考文献：
  名称：

  Stereospecific Access to β-Mannosides from Glucose-derived 1,2-Orthoesters as Glycosyl Donors

  摘要：

  A new, stereospecific synthesis of beta-mannosides from glucose-derived 1,2-orthoesters has been developed by a simple four step procedure, comprising beta-specific glycosidation of the 1,2-orthoesters, 2'-O-deacetylation, 2'-O-triflation, and SN 2 type inversion of the triflyl group providing beta-D-Man-(1-->6)-D-Gal, and beta-D-Man-(1-->4)-D-Glc derivatives in reasonable yield.

  DOI：

  10.3987/com-03-s60

文献信息

• Dehydroxy Substitution Reactions of the Anomeric Hydroxy Groups in Some Protected Sugars Initiated by Anodic Oxidation of Triphenylphosphine.
  作者：Hatsuo MAEDA、Sayaka MATSUMOTO、Takashi KOIDE、Hidenobu OHMORI

  DOI：10.1248/cpb.46.939

  日期：——

  The anodic transformation of 2, 3 : 5, 6-di-O-isopropylidene-α-D-mannofuranose (4) and 2, 3, 4, 6-tetra-O-benzyl-D-glucopyranose (5) to the corresponding alkoxy phosphonium ions induces dehydroxy substitution of the sugars at the anomeric positions. Their dehydroxy fluorination and chlorination has been achieved by constant-current electrolysis with CH2Cl2-1, 2-dimethoxyethane/Ph3P/Ph3PH·BF4 and with CH2Cl2/Ph3P/Et4N·Cl, respectively.The electrolysis in the presence of Ph3P has proved to serve O-glycosylation with 4 or 5 as a glycosyl donor, provided that an aliphatic alcohol as a glycosyl acceptor is a weaker nucleophile, such as (CF3)2CHOH, CF3CH2OH, and tert-BuOH, than the protected sugar toward Ph3P+· generated anodically from Ph3P. The present electrochemical reactions for 2, 3, 4, 6-tetra-O-acetyl-D-glucopyranose were unsuccessful, except for the dehydroxy chlorination.

  将 2, 3 : 5, 6-二-O-异亚丙基-α-D-甘露糖（4）和 2, 3, 4, 6-四-O-苄基-D-吡喃葡萄糖（5）阳极转化为相应的烷氧基鏻离子，可诱导糖类在异构体位置发生脱羟基取代。分别用 CH2Cl2-1，2-二甲氧基乙烷/Ph3P/Ph3PH-BF4 和 /Ph3P/Et4N-Cl 进行恒流电解，实现了它们的脱羟基氟化和氯化。事实证明，以 4 或 5 为糖基供体，在 Ph3P 存在下进行的电解可用于 O-糖基化，前提是作为糖基受体的脂肪醇（如 (CF3)2CHOH、 CH2OH 和 tert-BuOH）比受保护的糖对 Ph3P 阳极生成的 Ph3P+- 的亲核力更弱。除了脱羟基氯化反应外，2, 3, 4, 6-四-O-乙酰基-D-吡喃葡萄糖的电化学反应都不成功。