2-para-hydroxyphenyl-p-carborane | 379738-54-2

• 英文名称: 2-para-hydroxyphenyl-p-carborane
• CAS: 379738-54-2
• 化学式: C₈H₁₆B₁₀O
• 分子量: 236.324
• InChiKey: LUPWQUJFKLHYNO-UHFFFAOYSA-N

计算性质

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反应信息

• 作为产物：
  描述：

  2-iodo-closo-1,12-dodecaborane 、 4-甲氧基苯基溴化镁 在 bis-triphenylphosphine-palladium(II) chloride copper(l) iodide 作用下， 以 四氢呋喃 为溶剂， 以90%的产率得到2-(4-methoxyphenyl)-p-carborane
  参考文献：
  名称：

  Magnesium-assisted intramolecular demethylation utilizing carborane C–H geometry

  摘要：

  A novel type of demethylation reaction was designed in the Pd-catalyzed coupling reaction of iodocarboranes with several Grignard reagents, CH3OPhMgBr. 3-Iodo-o-carborane 1 reacted with 2-CH3OPhMgBr to afford the corresponding phenol compound 4b in 78% yield. However, when compound 1 was reacted with the other Grignard reagents, the corresponding methoxyl compounds 5a and 6a were obtained in excellent yields. 2-Iodo-p-carborane 3 reacted with 2-CH3OPhMgBr to afford the corresponding phenol 8b in 50% yield and the methoxyl compound 8a in 41% yield. The carborane C-H geometry, which can form an intramolecular C-H center dot center dot center dot O hydrogen bonding, seems to be an important factor in the demethylation process. To examine the mechanism of the demethylation, compounds 1 and 4a were treated with CH3MgBr and quenched with D2O. While the two C-Hs of compound 1 were completely deuterated, compound 4a showed a replacement of one C-H with C-D. Therefore, we propose a mechanism involving intramolecular C-Mg center dot center dot center dot O interaction instead of intramolecular C-H center dot center dot center dot O interaction, via the generation of 3-iodo-o-carboranyl(MgBr)(2), 11. Since it is also possible to replace the C-Hs with various metals other than Mg, new applications of carboranes in coordination and metal catalyst chemistry can be expected. (C) 2008 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2008.11.044