1-[1-methoxy-2-(2,6-dimethylphenyl)-imino]-2,3,4,6-tetra-O-acetyl-α-D-glucopyranoside | 221687-79-2

• 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-[1-methoxy-2-(2,6-dimethylphenyl)-imino]-2,3,4,6-tetra-O-acetyl-α-D-glucopyranoside
• 英文别名: [(2R,3R,4S,5R,6S)-3,4,5-triacetyloxy-6-[N-(2,6-dimethylphenyl)-C-methoxycarbonimidoyl]oxan-2-yl]methyl acetate
• CAS: 221687-79-2
• 化学式: C₂₄H₃₁NO₁₀
• 分子量: 493.511
• InChiKey: QENDUZPYSBWKHD-IFPLKCGESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  35
• 可旋转键数：
  12
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  136
• 氢给体数：
  0
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  1-[1-methoxy-2-(2,6-dimethylphenyl)-imino]-2,3,4,6-tetra-O-acetyl-α-D-glucopyranoside 在 盐酸 作用下， 以 四氢呋喃 为溶剂， 反应 16.0h， 以63%的产率得到1-[N-(2,6-dimethylphenyl)carbamoyl]-2,3,4,6-tetra-O-acetyl-α-D-glucopyranoside
  参考文献：
  名称：

  Radical-mediated imidoylation of telluroglycosides. Insertion of isonitriles into the glycosidic carbontellurium bond

  摘要：

  Telluroglycosides react with isonitrites under photo-thermal conditions to give 1-telluroimidoylglycosides. The reaction proceeds by atom transfer radical reaction to form an imidic C-Te bond, which can be substituted to a C-C band and C-O bond under oxidative conditions. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(99)00183-5
• 作为产物：
  描述：

  [(2R,3R,4S,5R)-3,4,5-triacetyloxy-6-(4-methylphenyl)tellanyloxan-2-yl]methyl acetate 在 lithium perchlorate 作用下， 以 二氯甲烷 、 氘代苯 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：

  Radical-mediated imidoylation of telluroglycosides. Insertion of isonitriles into the glycosidic carbontellurium bond

  摘要：

  Telluroglycosides react with isonitrites under photo-thermal conditions to give 1-telluroimidoylglycosides. The reaction proceeds by atom transfer radical reaction to form an imidic C-Te bond, which can be substituted to a C-C band and C-O bond under oxidative conditions. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(99)00183-5

文献信息

• 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.