2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl fluoride | 4163-40-0

• 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: 2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl fluoride
• 英文别名: Tetra-O-benzoyl-β-D-glucopyranosylfluorid；[(2R,3r,4s,5r,6s)-3,4,5-tribenzoyloxy-6-fluoro-tetrahydropyran-2-yl]methyl benzoate；[(2R,3R,4S,5R,6S)-3,4,5-tribenzoyloxy-6-fluorooxan-2-yl]methyl benzoate
• CAS: 4163-40-0
• 化学式: C₃₄H₂₇FO₉
• 分子量: 598.581
• InChiKey: OWVCLZCQOHOGFK-CMPUJJQDSA-N

物化性质

• 沸点：
  702.8±60.0 °C(Predicted)
• 密度：
  1.36±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  44
• 可旋转键数：
  13
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  114
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl fluoride 在 溴 、 potassium carbonate 作用下， 以 四氯化碳 为溶剂， 反应 5.0h， 以61%的产率得到tetra-O-benzoyl-5-bromo-β-D-glucopyranosyl fluoride
  参考文献：
  名称：

  L-己糖的选择性合成的替代导向策略：加快生产L-Idose的途径

  摘要：

  通过自由基还原功能化D-己糖来进行C-5差向异构化是获得稀有L-己糖的最快途径之一。借助DFT计算，我们证明了安装在D-葡萄糖系统中的β-F和C-6甲氧羰基都是优化L-ido产品立体选择性的关键。我们还提出了从商业上可获得的原料到L-idose衍生物的最短开发合成路线。

  DOI：

  10.1002/ejoc.202100042
• 作为产物：
  描述：

  (3aR,5R,6R,7S,7aR)-5-((benzoyloxy)methyl)-2-(pent-4-en-1-yloxy)-2-phenyltetrahydro-5H-[1,3]dioxolo[4,5-b]pyran-6,7-diyl dibenzoate 在 氟化氢吡啶 作用下， 以 二氯甲烷 为溶剂， 以94%的产率得到2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl fluoride
  参考文献：
  名称：

  Reaction of 1,2-Orthoesters with HF−Pyridine: A Method for the Preparation of Partly Unprotected Glycosyl Fluorides and Their Use in Saccharide Synthesis

  摘要：

  Glycosyl fluorides can be prepared In an efficient manner by treatment of pyranose- or furanose-derived 1,2-orthoesters, with hydrogen fluoride pyridine (HF-py). The method is compatible with the presence of a variety of protecting groups, including tert-butyldiphenyl silyl ethers, and can be applied to sugar derivatives with free hydroxyl groups, thus avoiding the need for the protection-deprotection steps.

  DOI：

  10.1021/ol901630d

文献信息

• The Fluorination (at C5) of Some Derivatives of D-Glucose
  作者：Brian W. Skelton、Robert V. Stick、Keith A. Stubbs、Andrew G. Watts、Allan H. White

  DOI：10.1071/ch03288

  日期：——

  presented.As well, various approaches to 5-fluoro glycopyranosides have been developed. The photobromination of phenyl tetra-O-acetyl-β-D-glucopyranoside, followed by fluorination and protecting group removal gave phenyl 5-fluoro-β-D-glucopyranoside. The photobromination of penta-O-acetyl-β-D-glucopyranose, followed by hydro- lysis and treatment with methanol, gave a hemiacetal that was converted via treatment

  β-D-吡喃葡萄糖和α-和β-D-吡喃葡萄糖基氟的各种过酯的光溴化反应产生了能够转化为相应的5-氟化物的5-溴衍生物。发现这种转化的最佳试剂是乙醚/二氯甲烷中的四氟硼酸银。介绍了五-O-苯甲酰基-5-氟-α-L-吡喃糖的单晶X射线结构测定。此外，还开发了5-氟吡喃糖苷的各种方法。苯基四-O-乙酰基-β-D-吡喃葡萄糖苷的光溴化作用，随后氟化和保护基团的去除得到苯基5-氟-β-D-吡喃葡萄糖苷。五-O-乙酰基-β-D-吡喃葡萄糖的光溴化，然后水解和甲醇处理，得到半缩醛，该半缩醛通过用二乙基氨基三氟化硫处理转化，随后保护基团去除为甲基5-氟-β-D-吡喃葡萄糖苷。甲基 2,3,4-tri-O-benzyl-6-deoxy-α- 和 -β-D-xylo-hex-5-enosides 用二甲基二环氧乙烷或 3-氯过苯甲酸转化为相应的环氧化物；随后用氟化氢/吡啶处理，然后产生5-氟吡喃糖苷作为主要产物。介绍了
• Catalytic and Stereoselective Glycosylation with Disarmed Glycosyl Fluoride Having Phthaloyl or Dichlorophthaloyl Protected Amino Function Using a 1 : 2 Combination of Stannic Chloride and Silver Tetrakis(pentafluorophenyl)borate
  作者：Hideki Jona、Hisashi Maeshima、Teruaki Mukaiyama

  DOI：10.1246/cl.2001.726

  日期：2001.7

  A catalytic and stereoselective glycosylation of various glycosyl acceptors with disarmed glycosyl fluorides having phthaloyl or dichlorophthaloyl protected amino function is successfully carried out by using a combination of stannic chloride (SnCl4) and silver tetrakis(pentafluorophenyl)borate [AgB(C6F5)4] in the coexistence of MS 5A, and the corresponding 1,2-trans disaccharides are obtained in high yields.

  通过使用氯化锡（SnCl4）和四氟苯基银四氟硼酸盐[AgB(C6F5)4]的组合，配合分子筛5A，可以成功催化和立体选择性地将各种糖苷受体与具有邻苯二甲酰保护氨基功能的弱活化糖苷氟化物进行糖苷化反应，得到相应的1,2-反式二糖，产率很高。
• Catalytic and Stereoselective Glycosylation with Disarmed Glycosyl Fluoride by Using a Combination of Stannous(II) Chloride (SnCl₂) and Silver Tetrakis(pentafluorophenyl)borate [AgB(C₆F₅)₄] as a Catalyst
  作者：Teruaki Mukaiyama、Hisashi Maeshima、Hideki Jona

  DOI：10.1246/cl.2001.388

  日期：2001.5

  A catalytic and stereoselective glycosylation of various glycosyl acceptors with disarmed glycosyl fluorides is successfully carried out by using a combination of stannous(II) chloride (SnCl2) and silver tetrakis(pentafluorophenyl)borate [AgB(C6F5)4] as a catalyst in the coexistence of MS5A in toluene and the corresponding 1,2-trans di- or trisaccharides were obtained in high yields.

  通过使用氯化亚锡 (II) (SnCl2) 和四（五氟苯基）硼酸银 [AgB(C6F5)4] 作为共存催化剂，成功地进行了各种糖基受体与脱臂糖基氟化物的催化和立体选择性糖基化MS5A 的甲苯溶液和相应的 1,2-反式二糖或三糖以高产率获得。
• Trifluoromethanesulfonic Acid (TfOH)-Catalyzed Stereoselective Glycosylation Using Glycosyl Fluoride
  作者：Teruaki Mukaiyama、Hideki Jona、Kazuya Takeuchi

  DOI：10.1246/cl.2000.696

  日期：2000.6

  Stereoselective glycosylation of 2-O-benzoyl-3,4,6-tri-O-benzyl-β-d-glucosyl fluoride 6 with several glycosyl acceptors is successfully carried out by using a catalytic amount of trifluoromethanesulfonic acid (TfOH).

  利用催化量的三氟甲磺酸（TfOH），成功地将 2-O-苯甲酰基-3,4,6-三-O-苄基-β-d-葡糖基氟化物 6 与多种糖基受体进行了立体选择性糖基化。
• GeCl₂·Dioxane–AgBF₄ Catalyzed Activation of Glycosyl Fluorides for Glycosylation
  作者：Qiuyu Zhu、Yu Tang、Biao Yu

  DOI：10.1021/acs.orglett.2c01146

  日期：2022.5.27

  catalytic glycosyl fluoride activation system using the GeCl2·dioxane–AgBF4 combination was developed, which involves a reversible activation of the anomeric C–F bond by a [Ge(II)–Cl]+ cation and a reversible chloride ion transfer between Ge(II) and glycosyl cations. This catalytic glycosylation system is easy to operate, proceeds at room temperature, and offers a broad scope of substrates.

  开发了一种使用 GeCl 2 ·二恶烷-AgBF 4组合的催化糖基氟化物活化系统，该系统涉及通过 [Ge(II)-Cl] +阳离子对异头 C-F 键的可逆活化和在它们之间的可逆氯离子转移。 Ge(II) 和糖基阳离子。这种催化糖基化系统易于操作，在室温下进行，并提供广泛的底物。