(1R,2S,5R)-(-)-1-Menthyl 2,3,4,6-tetra-O-benzoyl-β-D-glucopyranoside

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (1R,2S,5R)-(-)-1-Menthyl 2,3,4,6-tetra-O-benzoyl-β-D-glucopyranoside
• 英文别名: menthyl 2,3,4,6-tetra-O-benzoyl-β-D-glucopyranoside；menthyl 2,3,4,6-tetra-O-benzoyl-D-glucopyranoside；menthyl-(tetra-O-benzoyl-β-D-glucopyranoside)；Menthyl-(tetra-O-benzoyl-β-D-glucopyranosid)；[(2R,3R,4S,5R,6R)-3,4,5-tribenzoyloxy-6-[(1R,2S,5R)-5-methyl-2-propan-2-ylcyclohexyl]oxyoxan-2-yl]methyl benzoate
• 化学式: C₄₄H₄₆O₁₀
• 分子量: 734.843
• InChiKey: PGVGKTOVAJXXEY-CFDRKNAISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.8
• 重原子数：
  54
• 可旋转键数：
  16
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  124
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为产物：
  描述：

  1,2,3,4,6-五-o-苯甲酰基-beta-d-吡喃葡萄糖 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 三氟甲磺酸酐 、 三氟甲磺酸三甲基硅酯 、 二异丙胺 、 三苯基膦 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 生成 (1R,2S,5R)-(-)-1-Menthyl 2,3,4,6-tetra-O-benzoyl-β-D-glucopyranoside
  参考文献：
  名称：

  以邻(对甲氧基苯乙炔基)苄基糖苷为供体的Tf2O/TfOH催化糖基化及其在低聚糖合成中的应用

  摘要：

  使用 Tf 2 O 或 TfOH 作为催化剂并使用o -(对甲氧基苯基乙炔基) 苄基 (MPEB) 糖苷作为供体建立催化糖基化方案。MPEB 供体稳定且易于从廉价的起始材料制备。供体被 10 mol% Tf 2 O 或 TfOH 激活，并与各种受体偶联，以适度到良好的产率提供所需的糖苷。该糖基化方案通过“潜在活性”策略进一步应用于线性六甘露糖的合成。

  DOI：

  10.1016/j.tetlet.2023.154342

文献信息

• Glycosylation with 3,5-Dimethyl-4-(2′-phenylethynylphenyl)phenyl (EPP) Glycosides via a Dearomative Activation Mechanism
  作者：Zhifei Hu、Yu Tang、Biao Yu

  DOI：10.1021/jacs.9b00210

  日期：2019.3.27

  A highly effective and versatile glycosylation method is developed, which uses 3,5-dimethyl-4-(2'-phenylethynylphenyl)phenyl (EPP) glycosides as donors and NIS/TMSOTf as promoter and proceeds via an unprecedented dearomative activation mechanism.

  开发了一种高效且通用的糖基化方法，该方法使用 3,5-二甲基-4-(2'-苯基乙炔基苯基)苯基 (EPP) 糖苷作为供体，NIS/TMSOTf 作为启动子，并通过前所未有的脱芳基活化机制进行。
• 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。
• A Cu(OTf)₂-Catalyzed Glycosylation with Glycosyl <i>ortho</i>-<i>N</i>-Phthalimidoylpropynyl Benzoates as Donors
  作者：Bei-Bei Zhan、Kai-Sheng Xie、Qian Zhu、Weiping Zhou、Dapeng Zhu、Biao Yu

  DOI：10.1021/acs.orglett.3c01163

  日期：2023.6.2

  A Cu(OTf)2-catalyzed glycosylation protocol using glycosyl ortho-N-phthalimidoylpropynyl benzoates (NPPBs) as donors was disclosed, which features an inexpensive copper catalyst, operationally convenient conditions, high to excellent yields, and a broad substrate scope. Mechanistic studies indicated an isochromen-4-yl copper(II) intermediate arising from the departure of the leaving group.

  公开了一种使用糖基邻-N-邻苯二甲酰亚胺基丙炔基苯甲酸酯 (NPPB) 作为供体的Cu(OTf) 2催化糖基化方案，该方案具有廉价的铜催化剂、操作方便的条件、高至优异的产率和广泛的底物范围。机理研究表明离去基团的离去产生了 isochrome-4-yl copper(II) 中间体。
• Efficient <i>O</i>- and <i>S</i>-glycosylation with <i>ortho</i>-2,2-dimethoxycarbonylcyclopropylbenzyl thioglycoside donors by catalytic strain-release
  作者：Han Ding、Jian Lv、Xiao-Lin Zhang、Yuan Xu、Yu-Han Zhang、Xue-Wei Liu

  DOI：10.1039/d3sc06619c

  日期：2024.3.6

  facile chemical access to the challenging S-glycosides. Because the activation conditions of conventional glycosyl donors and our CCPB thioglycoside are orthogonal, our novel donor is amenable to controlled one-pot glycosylation reactions with conventional donors for expeditious access to complex glycans. The strain-release glycosylation is applied to the assembly of a tetrasaccharide of O-polysaccharide

  我们在此提出了一种使用合理设计的邻-2,2-二甲氧基羰基环丙基苄基（CCPB）硫代糖苷供体的菌株释放糖基化方法。供体通过温和 Sc(OTf) 3催化的远程可激活供体-受体环丙烷 (DAC) 的亲核开环而被激活。我们的新糖基化方法可有效合成O -、 N - 和S - 糖苷，为获得具有挑战性的S - 糖苷提供了简便的化学途径。由于传统糖基供体和我们的 CCPB 硫代糖苷的激活条件是正交的，因此我们的新型供体适合与常规供体进行受控的一锅糖基化反应，以快速获得复杂的聚糖。菌株释放糖基化应用于大肠杆菌O-33 O-多糖四糖的一锅组装及1,1'-S-连接糖苷口服半乳糖凝集素3（Gal-3）抑制剂的合成，TD139，证明构建O-和S-糖苷的新方法的多功能性和有效性。
• Tetra-O-benzoylglucosylation: A New 1H Nuclear Magnetic Resonance Method for Determination of the Absolute Configuration of Secondary Alcohols
  作者：Mar Trujillo、Ezequiel Q. Morales、Jesus T. Vazquez

  DOI：10.1021/jo00101a023

  日期：1994.11

  A new method for determination of the absolute configuration of secondary alcohols based on the anisotropic effect and glycosylation-induced H-1 NMR shifts is described. The tetra-O-benzoyl-beta-glucosylation of secondary alcohols induces dramatic shifts in the aglycon H-1 NMR peaks. The differences between the proton chemical shifts of the D-glucosylated derivative and the free alcohol (Delta delta = delta(D) - delta(ROH)) or more significantly between their chemical shifts in the D- and L-glucosylated derivatives (Delta delta = delta(D) - delta(L)) are characteristic of the absolute configuration of the secondary chiral alcohol. Furthermore, in most cases the sign of the chemical shift difference of the carbinyl protons correlates with the absolute configuration of their carbons, namely positive or negative Delta delta are obtained for (R)- or (S)-carbinyl carbons, respectively. Moreover, this method involves the use of one enantiomer and generally a single derivatization is sufficient.