N-(1,7-dicarba-closo-dodecaboran-9-yl)trifluoroacetamide | 1254975-66-0

• 英文名称: N-(1,7-dicarba-closo-dodecaboran-9-yl)trifluoroacetamide
• CAS: 1254975-66-0
• 化学式: C₄H₁₂B₁₀F₃NO
• 分子量: 255.251
• InChiKey: RNIHJJQMNUGLMT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  N-(1,7-dicarba-closo-dodecaboran-9-yl)trifluoroacetamide 在 NaOH 作用下， 以 四氢呋喃 、 甲醇 、 水 为溶剂， 以89%的产率得到9-amino-1,7-dicarba-closo-dodecaborane
  参考文献：
  名称：

  Novel Approach to Aminocarboranes by Mild Amidation of Selected Iodo-carboranes

  摘要：

  A mild protocol for the palladium-catalyzed Buchwald-Hartwig amidation of icosahedral carboranes is described. Employing 2-dicyclohexylphosphino-2'-(N,N-dimethylamino)biphenyl (1) as a ligand and K3PO4 as a base, benzamide, trifluoroacetamide, acetamide, and formamide were coupled to a series of mono- and di-iodo carboranes furnishing the respective carborane derivatives in good to excellent yields. Subsequent base-mediated saponification of the trifluoroacetamide derivatives was shown to provide the free aminocarboranes. The structures of N-(1,7-dicarba-closo-dodecaboran-9-y1)benzamide (8a), N-(1,7-dicarba-closo-dodecaboran-9-yl)trifluoroacetamide (8b), N-(1,12-dicarba-closo-dodecaboran-2-yl)benzamide (10a), N-(1,2-dicarba-closo-dodecaboran-9-yl)benzamide (12a), N-(1,2-dicarba-closo-dodecaboran-9-yl)acetamide (12c), N-(1,2-dicarba-closo-dodecaboran-9-yl)formamide (12d), N-(1,2-dicarba-closo-dodecaboran-3-yl)benzamide (13a), N,N'-(1,7-dicarba-closo-dodecaboran-9,10-diyl)dibenzamide (15a), and N,N'-(1,7-dicarba-closo-dodecaboran-9,10-diyl)bis(trifluoroacetamide) (15b) have been established through X-ray single-crystal diffraction studies.

  DOI：

  10.1021/ic101620h
• 作为产物：
  描述：

  9-iodo-1,7-dicarba-closo-dodecaborane 、 2,2,2-三氟乙酰胺 在 potassium phosphate 、 XPhosPdCl{Hg(9-B-o-C₂B₁₀H₁₁)} * 0.5(THF) 、 2-二环己基磷-2,4,6-三异丙基联苯 作用下， 反应 2.0h， 生成 N-(1,7-dicarba-closo-dodecaboran-9-yl)trifluoroacetamide
  参考文献：
  名称：

  二十面体碳硼烷锻造不支持的金属-芳基键

  摘要：

  与可用于在芳族烃上安装官能团的多种金属催化交叉偶联方法相反，对于二十面体碳硼烷，目前尚没有可比较的各种方法，它们是富含硼的芳基的三维芳族类似物。部分原因是由于对碳硼烷交叉偶联基本步骤的了解有限。在这里，我们报告了我们在分离金属-硼基配合物方面的努力，以加深我们对这些基本步骤之一的认识，即氧化加成。10 M组的结构特征示例具有二十面体碳硼烷的-B键是完全未知的。使用巯基碳氧烷作为传递M-B键的试剂，发现铂和钯的反应性不同，前者分离出Pt-B键，而后者形成了罕见的Pd-Hg键。

  DOI：

  10.1002/chem.201601292

文献信息

• B–N, B–O, and B–CN Bond Formation via Palladium-Catalyzed Cross-Coupling of B-Bromo-Carboranes
  作者：Rafal M. Dziedzic、Liban M. A. Saleh、Jonathan C. Axtell、Joshua L. Martin、Simone L. Stevens、A. Timothy Royappa、Arnold L. Rheingold、Alexander M. Spokoyny

  DOI：10.1021/jacs.6b05505

  日期：2016.7.27

  Carboranes are boron-rich molecules that can be functionalized through metal-catalyzed cross coupling. Here, for the first time, we report the use of bromo-carboranes in palladium-catalyzed cross-coupling for efficient B-N, B-O, and unprecedented B-CN bond formation. In many cases bromo-carboranes outperform the traditionally utilized iodo-carborane species. This marked difference in reactivity is leveraged to circumvent multistep functionalization by directly coupling small nucleophiles (-OH,-NH2, and -CN) and multiple functional groups onto the boron-rich clusters.