1-p-methylphenyltelluro-2,3,4,6-tetra-O-benzoyl-β-D-glucopyranoside | 183367-63-7

• 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: 1-p-methylphenyltelluro-2,3,4,6-tetra-O-benzoyl-β-D-glucopyranoside
• 英文别名: [(2R,3R,4S,5R,6S)-3,4,5-tribenzoyloxy-6-(4-methylphenyl)tellanyloxan-2-yl]methyl benzoate
• CAS: 183367-63-7
• 化学式: C₄₁H₃₄O₉Te
• 分子量: 798.316
• InChiKey: DTRRCCNZCPDKIO-WIESDFACSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.58
• 重原子数：
  51
• 可旋转键数：
  15
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  114
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  1-p-methylphenyltelluro-2,3,4,6-tetra-O-benzoyl-β-D-glucopyranoside 以 氘代苯 为溶剂， 反应 2.0h， 生成 [(2R,3R,4S,5R,6R)-3,4,5-tribenzoyloxy-6-(4-methylphenyl)tellanyloxan-2-yl]methyl benzoate
  参考文献：
  名称：

  在光化学和热条件下从碲糖苷可逆地产生糖基自由基

  摘要：

  在光解和热解后，1-β-碲脲糖苷异构化为α-异构体。异构化遵循一级反应动力学，并通过均相的CTe键裂解而通过糖基自由基中间体进行。如此产生的自由基被TEMPO自由基分子间捕获，表明糖基自由基是通过非链机制有效产生的。

  DOI：

  10.1016/s0040-4039(99)00181-1
• 作为产物：
  描述：

  [(2R,3R,4S,5R,6R)-3,4,5-tribenzoyloxy-6-(4-methylphenyl)tellanyloxan-2-yl]methyl benzoate 以 氘代苯 为溶剂， 反应 0.6h， 生成 1-p-methylphenyltelluro-2,3,4,6-tetra-O-benzoyl-β-D-glucopyranoside
  参考文献：
  名称：

  在光化学和热条件下从碲糖苷可逆地产生糖基自由基

  摘要：

  在光解和热解后，1-β-碲脲糖苷异构化为α-异构体。异构化遵循一级反应动力学，并通过均相的CTe键裂解而通过糖基自由基中间体进行。如此产生的自由基被TEMPO自由基分子间捕获，表明糖基自由基是通过非链机制有效产生的。

  DOI：

  10.1016/s0040-4039(99)00181-1

文献信息

• Combinatorial Synthesis of an Oligosaccharide Library by Using β-Bromoglycoside-Mediated Iterative Glycosylation of Selenoglycosides: Rapid Expansion of Molecular Diversity with Simple Building Blocks
  作者：Shigeru Yamago、Takeshi Yamada、Hiroki Ito、Osamu Hara、Yosuke Mino、Jun-ichi Yoshida

  DOI：10.1002/chem.200500126

  日期：2005.10.21

  new method for constructing an oligosaccharide library composed of structurally defined oligosaccharides is presented based on an iterative glycosylation of selenoglycosides. Treatment of 2-acyl-protected selenoglycosides with bromine selectively generates beta-bromoglycosides, which serve as glycosyl cation equivalents in the oligosaccharide synthesis. Thus, the coupling of the bromoglycosides with

  基于硒代糖苷的迭代糖基化，提出了一种构建由结构定义的寡糖组成的寡糖文库的新方法。用溴处理2-酰基保护的硒代糖苷可选择性生成β-溴代糖苷，其在寡糖合成中充当糖基阳离子等同物。因此，溴糖苷与另一硒代糖苷的偶联提供了相应的糖基化硒代糖苷，其可以直接用于下一个糖基化。该序列的迭代允许合成多种寡糖，包括激发子活性七糖。迭代糖基化的特征是，在与糖基受体偶联之前，可以通过活化糖基供体选择性地偶联糖基供体和具有相同端基反应性的受体。因此，相同的硒代糖苷可用于糖基供体和受体。通过针对激发子活性寡糖的寡糖文库的构建来举例说明该特征。可以从简单的硒糖苷开始构建由立体化学定义的寡糖组成的具有相当大的结构多样性的文库。该特征已通过构建针对激发子活性寡糖的寡糖文库来举例说明。可以从简单的硒糖苷开始构建由立体化学定义的寡糖组成的具有相当大的结构多样性的文库。通过针对激发子活性寡糖的寡糖文库的构建来举例说明该特征。可以从
• Electrochemistry of Chalcogenoglycosides. Rational Design of Iterative Glycosylation Based on Reactivity Control of Glycosyl Donors and Acceptors by Oxidation Potentials
  作者：Shigeru Yamago、Koji Kokubo、Osamu Hara、Sadayoshi Masuda、Jun-ichi Yoshida

  DOI：10.1021/jo0261350

  日期：2002.11.1

  also affected by the para-substituents, and the substitution effect correlates very well with the HOMO energy of para-substituted benzenechalcogenol and with the Hammett sigma p + value. Electrochemical glycosylation of telluroglycosides has been examined, and it was found that the use of an undivided cell is more effective than the use of a divided cell. Selective activation of the chalcogenoglycosides

  已经研究了带有乙酰，苯甲酰基和苄基保护基的各种对位取代的苯硫基-，苯基硒基-和苯基碲-吡喃葡萄糖基吡喃糖苷的电化学性质，以估计硫属糖苷对电化学糖基化的反应性。硫族糖苷的氧化电位与硫属元素原子的电离电位显示出良好的相关性，并以硫代，硒代和碲糖苷的顺序降低。它也受到对位取代基的影响，并且取代作用与对位取代苯硫属元素醇的HOMO能量以及Hammettσp +值非常相关。已经检查了碲糖苷的电化学糖基化，并且发现使用未分裂的细胞比使用分裂的细胞更有效。已经检查了基于其氧化电位的硫磺糖苷在本体电解中的选择性活化，并且可以从其氧化电位估算碲糖苷的相对反应性。但是，硒代糖苷在制备糖基化反应中的相对反应性对氧化电位值不敏感。
• Glycosylation with telluroglycosides. Stereoselective construction of α- and β-anomers
  作者：Shigeru Yamago、Koji Kokubo、Hideo Murakami、Yosuke Mino、Osamu Hara、Jun-ichi Yoshida

  DOI：10.1016/s0040-4039(98)01753-5

  日期：1998.10

  Telluroglycosides are activated under neutral conditions and serve as excellent glycosyl donors in the glycosylation reaction. Both α- and β-anomers are selectively formed by the proper choice of the C-2 protecting group and solvent.

  碲糖苷在中性条件下被激活，并在糖基化反应中充当出色的糖基供体。两个α-和β端基异构体是由C-2保护基，溶剂的适当选择有选择地形成。
• <i>O</i>-Glycosidation of Telluroglycoside by Electrochemical Oxidation
  作者：Shigeru Yamago、Koji Kokubo、Jun-ichi Yoshida

  DOI：10.1246/cl.1997.111

  日期：1997.2

  The electrochemical oxidation of telluroglycosides in the presence of primary or secondary alcohols results the O-glycosidation with high efficiency. Difference of the oxidation potential is nicely accounted for that of the reactivity of armed- and disarmed-telluroglycosides.

  在初级或次级醇存在下，碲糖苷的电化学氧化导致高效的O-糖苷化。氧化电位的差异很好地解释了具备和缺乏活性的碲糖苷的反应性差异。
• Synthetic and Theoretical Studies on Group-Transfer Imidoylation of Organotellurium Compounds. Remarkable Reactivity of Isonitriles in Comparison with Carbon Monoxide in Radical-Mediated Reactions
  作者：Shigeru Yamago、Hiroshi Miyazoe、Ryuta Goto、Masahiro Hashidume、Takashi Sawazaki、Jun-ichi Yoshida

  DOI：10.1021/ja003879r

  日期：2001.4.1

  Imidoylation of organotellurium compounds with isonitriles has been investigated in conjunction with the radical-mediated C1 homologation reaction by using CO and isonitriles. Carbon-centered radicals generated photochemically or thermally from organotellurium compounds react with isonitriles in a group-transfer manner to give the corresponding imidoylated products. Organotellurium compounds have been found to serve as effective precursors of a wide variety of stabilized radicals, namely benzyl, alpha -alkoxy, alpha -amino, and acyl radicals, which take part in the imidoylation with high efficiency. The reactions are compatible with various functional groups, and can be carried out in various solvents including environmentally benign water. The reactivity of isonitriles has been compared with that of CO through competition experiments, and the results indicate that isonitriles are superior to CO as radical accepters in reactions with stabilized radicals. The origin of the differences has been addressed in theoretical studies with density functional theory calculations using the B3LYP hybrid functional. The calculations suggest that both carbonylation and imidoylation proceed with low activation energies, and that there an virtually no differences in the kinetic sense, instead, it indicates that thermodynamic effects, namely differences in the stability of the acyl and the imidoyl radicals, control the overall course of the reactions.