2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl N-phenyltrifluoroacetimidate | 1371597-38-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl N-phenyltrifluoroacetimidate
• 英文别名: 2,3,4,6-tetra-O-benzyl-D-glucopyranosyl N-phenyl-2,2,2-trifluoroacetimidate
• CAS: 1371597-38-4
• 化学式: C₄₂H₄₀F₃NO₆
• 分子量: 711.778
• InChiKey: BJCRNHIPUWZUPQ-JSMBFNCYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.99
• 重原子数：
  52.0
• 可旋转键数：
  15.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  67.74
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl N-phenyltrifluoroacetimidate 、 benzyl 3-O-acetyl-2-deoxy-2-(2,2,2-trichloroethyloxycarbonyl)-amino-4,6-O-(di-tert-butylsilanediyl)-α-D-galactosamine-(1→2)-4,6-di-O-benzylidene-β-D-mannopyranosyl-(1→4)-3,6-di-O-benzyl-2-O-[2-O-acetyl-3-O-benzyl-4,6-di-O-benzylidene-β-D-glucopyranosyl-(1→2)]-α-D-mannopyranosyl-(1→5)-[N-benzyloxycarbonyl-3-aminopropyl-4-O-benzyl-3-deoxy-7,8-O-isopropylidene-α-D-manno-octulopyranosid]onate 在 2,6-二叔丁基-4-甲基吡啶 、 三氟甲磺酸 作用下， 以 乙醚 为溶剂， 以73%的产率得到benzyl 3-O-acetyl-2-deoxy-2-(2,2,2-trichloroethyloxycarbonyl)-amino-4,6-O-(di-tert-butylsilanediyl)-α-D-galactosamine-(1→2)-4,6-di-O-benzylidene-3-O-[2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl-(1→3)]-β-D-mannopyranosyl-(1→4)-3,6-di-O-benzyl-2-O-[2-O-acetyl-3-O-benzyl-4,6-di-O-benzylidene-β-D-glucopyranosyl-(1→2)]-α-D-mannopyranosyl-(1→5)-[N-benzyloxycarbonyl-3-aminopropyl-4-O-benzyl-3-deoxy-7,8-O-isopropylidene-α-D-mannooctulopyranosid]onate
  参考文献：
  名称：

  Chemical Synthesis and Immunological Evaluation of the Inner Core Oligosaccharide of Francisella tularensis

  摘要：

  Francisella tularensis, which is a Gram negative bacterium that causes tularemia, has been classified by the Center for Disease Control and Prevention (CDC) as a category A bioweapon. The development of vaccines, immunotherapeutics, and diagnostics for F. tularensis requires a detailed knowledge of the saccharide structures that can be recognized by protective antibodies. We have synthesized the inner core region of the lipopolysaccharide (LPS) of F. tularensis to probe antigenic responses elicited by a live and subunit vaccine. The successful preparation of the target compound relied on the use of a disaccharide which was modified by the orthogonal protecting groups diethylisopropylsilyl (DEIPS), 2-naphthylmethyl (Nap), allyl ether (All), and levulinoyl (Lev) ester. The ability to remove the protecting groups in different orders made it possible to establish the optimal glycosylations sequence to prepare a highly crowded 1,2,3-cis configured branching point. A variety of different methods were exploited to control anomeric selectivities of the glycosylations. A comparison of the H-1 NMR spectra of isolated material and the synthetic derivative confirmed the reported structural assignment of the inner core oligosaccharide of F. tularensis. The observation that immunizations with LPS lead to antibody responses to the inner core saccharides provides an impetus to further explore this compound as a vaccine candidate.

  DOI：

  10.1021/ja306274v
• 作为产物：
  描述：

  苯基2,3,4,6-四-O-苄基-1-硫代-beta-D-吡喃葡萄糖苷 在 N-溴代丁二酰亚胺(NBS) 、 水 、 potassium carbonate 作用下， 以 丙酮 为溶剂， 反应 1.58h， 生成 2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl N-phenyltrifluoroacetimidate
  参考文献：
  名称：

  在 C2 和 C3 羟基上带有环状保护的 1,2-反式选择性糖基供体

  摘要：

  描述了一种新的 1,2-反式选择性糖基化反应。葡萄糖基供体在 C-2 和 C-3 羟基上被循环保护为六（丁烷二缩醛）、七（四异丙基二亚硅氧烷）或八（2,3-o-亚二甲苯基）元稠环，以直接方式合成. 在常规反应条件下，葡萄糖基供体与各种受体的糖基化反应主要生成β-糖苷。结果表明，从立体选择性和化学稳定性的角度来看，邻二甲苯基是合适的1,2-反式导向基团。通过核磁共振光谱和计算模拟对邻二甲苯保护的葡萄糖衍生物的氧代碳鎓离子进行了构象研究。结果表明氧碳鎓离子主要采用 4H3 构象，这是由于 C-2 和 C-3 处的刚性互稠环，而非环状保护的衍生物可能在构象之间波动。这些结果表明，C-2 处的伪赤道木氧基与传入的亲核试剂之间的相互作用阻碍了 1,2-顺式攻击。

  DOI：

  10.1002/ejoc.201700671

文献信息

• Cholesteryl 6-<i>O</i>-acyl-α-glucosides from diverse <i>Helicobacter</i> spp. signal through the C-type lectin receptor Mincle
  作者：Dylan G. M. Smith、Emi Ito、Sho Yamasaki、Spencer J. Williams

  DOI：10.1039/d0ob01776k

  日期：——

  Stereoselective α-glucosylation of cholesterol enabled synthesis of cholesteryl 6-O-acyl-glucosides from diverse Helicobacter spp. and demonstration that they signal through the innate immune receptor Mincle.

  具有立体选择性的胆固醇α-葡萄糖基化使得从不同的幽门螺杆菌（Helicobacter spp.）中合成胆固醇6-O-酰基葡萄糖苷成为可能，并且证明它们通过固有免疫受体Mincle发出信号。
• Synthesis of Cage‐Shaped Borates Bearing Pyrenylmethyl Groups: Efficient Lewis Acid Catalyst for Photoactivated Glycosylations Driven by Intramolecular Excimer Formation
  作者：Yuya Tsutsui、Daiki Tanaka、Yoshiyuki Manabe、Yuka Ikinaga、Kumpei Yano、Koichi Fukase、Akihito Konishi、Makoto Yasuda

  DOI：10.1002/chem.202202284

  日期：2022.11.7

  groups was synthesized. The obtained 3aB functioned as a photoactivated Lewis acid catalyst. The photoactivation originates from the deformation of the cage-shaped scaffold driven by intramolecular excimer formations of the pyrenes, allowing the catalytic O-glycosylation using glycosyl fluorides to proceed with a high efficiency.

  合成了具有芘基甲基的笼形硼酸盐3a B 。得到的3a B 起光活化路易斯酸催化剂的作用。光活化源于由芘的分子内准分子形成驱动的笼形支架的变形，从而允许使用糖基氟化物的催化O-糖基化以高效率进行。
• Regenerative Glycosylation under Nucleophilic Catalysis
  作者：Swati S. Nigudkar、Keith J. Stine、Alexei V. Demchenko

  DOI：10.1021/ja411746a

  日期：2014.1.22

  This article describes 3,3-difluoroxindole (HOFox)-mediated glycosylation. The uniqueness of this approach is that both the in situ synthesis of 3,3-difluoro-3H-indol-2-yl (OFox) glycosyl donors and activation thereof can be conducted in a regenerative fashion as is a typical reaction performed under nucleophilic catalysis. Only a catalytic amount of the OFox imidate donor and a Lewis acid activator are present in the reaction medium. The OFox imidate donor is constantly regenerated upon its consumption until glycosyl acceptor has reacted.