2,3,4,6-tetra-O-benzoyl-α-D-mannopyranosyl fluoride | 3825-18-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,3,4,6-tetra-O-benzoyl-α-D-mannopyranosyl fluoride
• 英文别名: Tetra-O-benzoyl-α-D-mannopyranosyl-fluorid；a-D-Mannopyranosyl fluoride, tetrabenzoate；[(2R,3R,4S,5S,6R)-3,4,5-tribenzoyloxy-6-fluorooxan-2-yl]methyl benzoate
• CAS: 3825-18-1
• 化学式: C₃₄H₂₇FO₉
• 分子量: 598.581
• InChiKey: OWVCLZCQOHOGFK-ZNOUKXQUSA-N

物化性质

• 熔点：
  129-131 °C(Solv: ethyl ether (60-29-7); pentane (109-66-0))
• 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-α-D-mannopyranosyl fluoride 在 溴 、 potassium carbonate 、 三乙基硼 、 三正丁基氢锡 作用下， 以 四氯化碳 、 正己烷 、 甲苯 为溶剂， 生成 2,3,4-tri-O-benzoyl-5-C-benzoyloxy-6-deoxy-α-D-mannopyranosyl fluoride
  参考文献：
  名称：

  d-吡喃甘露糖基氟化物的 C-5 差向异构化：异头构型对自由基反应性的影响

  摘要：

  迄今为止，氟导向效应已被用来为稀有化合物提供短而有效的合成路线。我-伊多糖。然而，异头构型对其成功的重要性尚未得到实验验证。我们现在报道了α-和β-构型全O-苯甲酰化吡喃甘露糖基氟化物的合成，并初步表明它们对光溴化的反应性强烈依赖于异头构型。然后，通过揭示分离的 5- C-溴糖的自由基还原观察到的立体选择性的显着差异，验证了氟导向效应的立体化学基础。这项工作重要的是提供了一种供体功能化衍生物的合成路线我-古洛糖并揭示了对糖基自由基行为的新见解。

  DOI：

  10.1055/a-2149-4586
• 作为产物：
  描述：

  1,2-O-(α-methoxybenzylidene)-3,4,6-tri-O-benzoyl-β-D-mannopyranose 在 氟化氢吡啶 作用下， 以 二氯甲烷 为溶剂， 以98%的产率得到2,3,4,6-tetra-O-benzoyl-α-D-mannopyranosyl 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

• IPy₂BF₄/HF-Pyridine:  A New Combination of Reagents for the Transformation of Partially Unprotected Thioglycosides and <i>n</i>-Pentenyl Glycosides to Glycosyl Fluorides
  作者：J. Cristóbal López、Paloma Bernal-Albert、Clara Uriel、Serafín Valverde、Ana M. Gómez

  DOI：10.1021/jo7018653

  日期：2007.12.1

  The combination of bis(pyridinium)iodonium (I) tetrafluoroborate (IPy2BF4), and hydrogen fluoride pyridine (HF-py) forms an iodine monofluoride (IF) synthetic equivalent that can be used in the preparation of partially unprotected glycosyl fluorides from partially unprotected n-pentenyl glycosides and thioglycosides, thus avoiding the need for the protection/deprotection steps normally required in

  四氟硼酸双（吡啶）碘鎓（I）（IPy 2 BF 4）和氟化氢吡啶（HF-py）的组合形成碘一氟化物（IF）合成等价物，可用于制备部分未保护的糖基氟化物部分未保护的正戊烯基糖苷和巯基糖苷，因此避免了通常需要在该转化中进行的保护/去保护步骤。
• Reactions with and in anhydrous hydrogen fluoride systems. Part 8. Triethylamine trishydrofluoride — a convenient reagent for the stereoselective synthesis of glycosyl fluorides
  作者：Ralf Miethchen、Gundula Kolp

  DOI：10.1016/s0022-1139(00)82194-6

  日期：1993.1

  Stereoselective fluorinations are effected by bromine—fluorine exchange at glycosyl bromides of the D- and L-series using triethylamine trishydrofluoride. Pyranosyl fluorides of D-xylose, L-arabinose, D-glucose, D-mannose and L-rhamnose derivatives, as well as of D-galacturonic acid esters, have been prepared. The influence of neighbouring groups in the 2-position is considered.

  立体选择性氟化是通过使用三乙胺三氢氟化物在D系列和L系列的糖基溴上进行溴-氟交换来实现的。已经制备了D-木糖，L-阿拉伯糖，D-葡萄糖，D-甘露糖和L-鼠李糖衍生物以及D-半乳糖醛酸酯的吡喃磺酰氟。考虑在2位上相邻基团的影响。
• Glycosyl fluorides from <i>n</i>-pentenyl-related glycosyl donors — Application to glycosylation strategies
  作者：Bert Fraser-Reid、J. Cristobal Lopez、Paloma Bernal-Albert、Ana M. Gomez、Clara Uriel、Juan Ventura

  DOI：10.1139/cjc-2012-0285

  日期：2013.1

  fluorides by a variety of methods. In the case of NPGs, Barluenga’s reagent, bis(pyridinium)iodonium(I)tetrafluoroborate (IPy2BF4), gives good yields of glycosyl fluorides when HF–pyridine complex is used as an additional fluoride source. NPOEs can be activated either by a combination of electrophilic iodonium (Barluenga’s reagent) and HBF4 or by the action of HF–pyridine complex. The ensuing glycosyl

  正戊烯基糖苷 (NPG) 和正戊烯基原酸酯 (NPOE) 已通过多种方法转化为糖基氟。在 NPG 的情况下，当使用 HF-吡啶复合物作为额外的氟化物来源时，Barluenga 试剂双（吡啶鎓）碘鎓（I）四氟硼酸盐（IPy2BF4）可产生良好的糖基氟化物产率。NPOE 可以通过亲电子碘鎓（Barluenga 试剂）和 HBF4 的组合或通过 HF-吡啶复合物的作用被激活。当遇到 NPG 时，随之而来的糖基氟化物会形成一对半正交的糖基供体。
• IPy₂BF₄-Mediated Transformation of <i>n</i>-Pentenyl Glycosides to Glycosyl Fluorides:  A New Pair of Semiorthogonal Glycosyl Donors
  作者：J. Cristóbal López、Clara Uriel、Alejandra Guillamón-Martín、Serafín Valverde、Ana M. Gómez

  DOI：10.1021/ol070753r

  日期：2007.7.1

  Bis(pyridinium) iodonium(I) tetrafluoroborate (IPy2BF4), a solid and stable reagent, can be used to transform n-pentenyl orthoesters (NPOEs) and n-pentenyl glycosides (NPGs) into glycosyl fluorides. The latter pair constitutes a new set of semiorthogonal glycosyl donors that can be used in glycosylation strategies, alone or in combination with NPOEs.

  固态且稳定的试剂双吡啶鎓碘鎓（I）四氟硼酸酯（IPy2BF4）可用于将正戊烯基原酸酯（NPOE）和正戊烯基糖苷（NPG）转化为糖基氟化物。后者构成了一组新的半正交糖基供体，可单独或与NPOE结合用于糖基化策略。
• Revisiting Glycosylations Using Glycosyl Fluoride by BF₃·Et₂O: Activation of Disarmed Glycosyl Fluorides with High Catalytic Turnover
  作者：Yoshiyuki Manabe、Takuya Matsumoto、Yuka Ikinaga、Yuya Tsutsui、Shota Sasaya、Yuichiro Kadonaga、Akihito Konishi、Makoto Yasuda、Tomoya Uto、Changhao Dai、Kumpei Yano、Atsushi Shimoyama、Ayana Matsuda、Koichi Fukase

  DOI：10.1021/acs.orglett.1c03233

  日期：2022.1.14

  Catalytic glycosylations with glycosyl fluorides using BF3·Et2O are presented. Glycosylations with both armed and disarmed donors were efficiently catalyzed by 1 mol% of BF3·Et2O in a nitrogen-filled glovebox without the use of dehydrating agents. Our finding is in sharp contrast with conventional BF3·Et2O-mediated glycosylations, where excess Lewis acid and additives are required. Mechanistic studies

  介绍了使用 BF 3 ·Et 2 O与糖基氟化物的催化糖基化。在没有使用脱水剂的情况下，在充满氮气的手套箱中，1 mol% 的 BF 3 ·Et 2 O有效地催化了武装和解除武装供体的糖基化。我们的发现与传统的 BF 3 ·Et 2 O 介导的糖基化形成鲜明对比，后者需要过量的路易斯酸和添加剂。机理研究表明，由原位生成的 HF 和玻璃容器反应形成的化学物质参与了催化循环。