1-p-methylphenyltelluro-2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside | 183367-67-1

• 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-acetyl-β-D-glucopyranoside
• 英文别名: [(2R,3R,4S,5R,6S)-3,4,5-triacetyloxy-6-(4-methylphenyl)tellanyloxan-2-yl]methyl acetate
• CAS: 183367-67-1
• 化学式: C₂₁H₂₆O₉Te
• 分子量: 550.032
• InChiKey: VMBJHVWZEDZXDT-ADAARDCZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.41
• 重原子数：
  31
• 可旋转键数：
  11
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.52
• 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-acetyl-β-D-glucopyranoside 在 lithium perchlorate 作用下， 以 甲醇 、 苯 为溶剂， 反应 5.0h， 生成 1-[1-methoxy-2-(2,6-dimethylphenyl)-imino]-2,3,4,6-tetra-O-acetyl-α-D-glucopyranoside
  参考文献：
  名称：

  Synthetic and Theoretical Studies on Group-Transfer Imidoylation of Organotellurium Compounds. Remarkable Reactivity of Isonitriles in Comparison with Carbon Monoxide in Radical-Mediated Reactions

  摘要：

  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.

  DOI：

  10.1021/ja003879r
• 作为产物：
  描述：

  Acetic acid (2R,3R,4S,5R,6R)-4,5-diacetoxy-6-acetoxymethyl-2-p-tolyltellanyl-tetrahydro-pyran-3-yl ester 以 氘代乙腈 为溶剂， 反应 2.0h， 生成 1-p-methylphenyltelluro-2,3,4,6-tetra-O-acetyl-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

• 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。
• <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。
• Arylthiols as Highly Chemoselective and Environmentally Benign Radical Reducing Agents
  作者：Shigeru Yamago、Atsushi Matsumoto

  DOI：10.1021/jo801200b

  日期：2008.9.19

  Arylthiols serve as excellent environmentally benign reducing agents for organotellurium, organostibine, and organobismuthine compounds under radical conditions. Both small molecules and macromolecules possessing these heteroatorn groups are reduced under moderate thermal conditions to give near quantitative yields in most cases. The reduction shows high chemoselectivity with respect to the heteroatorn compounds the reactivity decreases in the order alkylbismuthines, alkylstibines, and alkyltellurides, while simple alkyl iodides could not be reduced. Alkyltellurides are selectively reduced in the presence of alkyl iodides even when an excess amount of arylthiol is used. Furthermore, alkylstibines are also selectively reduced in the presence of alkyltellurides. Moreover, the reduction conditions are compatible with the presence of a variety of polar functional groups in the substrates, products, and solvents, which are not tolerant under ionic and metal-catalyzed conditions. Carbon-carbon bond formation is possible with use of the carbon-centered radicals that are generated. The results clearly reveal the synthetic utility of arylthiols in organic synthesis.