[(Py3CH)PdIV(4'-tert-butyl-2',6'-dideutero-5-fluoro-[1,1'-biphenyl]-2-yl)(Cl)2][OTf] | 1431223-78-7

• 英文名称: [(Py3CH)PdIV(4'-tert-butyl-2',6'-dideutero-5-fluoro-[1,1'-biphenyl]-2-yl)(Cl)2][OTf]
• 英文别名: [(Py₃CH)Pd^IV(4'-tert-butyl-2',6'-dideutero-5-fluoro-[1,1'-biphenyl]-2-yl)(Cl)₂][OTf]
• CAS: 1431223-78-7
• 化学式: CF₃O₃S*C₃₂H₂₉Cl₂FN₃Pd
• 分子量: 802.981
• InChiKey: VYDDOZYNJURBAJ-MKZXEAOQSA-K

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：

  [(Py3CH)PdIV(4'-tert-butyl-2',6'-dideutero-5-fluoro-[1,1'-biphenyl]-2-yl)(Cl)2][OTf] 在 silver(I) acetate 作用下， 以 氯仿 为溶剂， 反应 0.75h， 以63%的产率得到[(Py3CH)PdIV(4'-tert-butyl-2'-deutero-5-fluoro-[1,1'-biphenyl]-2,2’-diyl)(Cl)][OTf]
  参考文献：
  名称：

  A Detailed Study of Acetate-Assisted C–H Activation at Palladium(IV) Centers

  摘要：

  This report describes a detailed investigation of acetate-assisted C-H activation at Pd-IV centers supported by the tris(2-pyridyl)-methane (Py3CH) ligand. Mechanistic information about this transformation has been obtained through the following:, (i) extensive one- and two-dimensional NMR analysis, (ii) reactivity studies of a series of substituted analogues, and (iii) isotope effect studies. These experiments all suggest that C-H activation at [(Py3CH)Pd-IV(biphenyl)Cl-2)(+) occurs via a multistep process involving chloride-to-acetate ligand exchange followed by conformational and configurational isomerization and then C-H cleavage. The data also suggest that C-H cleavage proceeds via an acetate-assisted mechanism with the carboxylate likely serving as an intramolecular base. The viability of acetate-assisted C-H activation at high valent palladium has important implications for the design and optimization of catalytic processes involving this transformation as a key step.

  DOI：

  10.1021/ja401557m
• 作为产物：
  描述：

  1,6-dideutero-4-(tert-butyl)-iodobenzene 在 4-叔丁基吡啶 、 盐酸 、 bis-triphenylphosphine-palladium(II) chloride 、 正丁基锂 、 potassium carbonate 、 sodium nitrite 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 甲醇 、 正己烷 、 二氯甲烷 、 氯仿 、 水 为溶剂， 反应 8.41h， 生成 [(Py3CH)PdIV(4'-tert-butyl-2',6'-dideutero-5-fluoro-[1,1'-biphenyl]-2-yl)(Cl)2][OTf]
  参考文献：
  名称：

  A Detailed Study of Acetate-Assisted C–H Activation at Palladium(IV) Centers

  摘要：

  This report describes a detailed investigation of acetate-assisted C-H activation at Pd-IV centers supported by the tris(2-pyridyl)-methane (Py3CH) ligand. Mechanistic information about this transformation has been obtained through the following:, (i) extensive one- and two-dimensional NMR analysis, (ii) reactivity studies of a series of substituted analogues, and (iii) isotope effect studies. These experiments all suggest that C-H activation at [(Py3CH)Pd-IV(biphenyl)Cl-2)(+) occurs via a multistep process involving chloride-to-acetate ligand exchange followed by conformational and configurational isomerization and then C-H cleavage. The data also suggest that C-H cleavage proceeds via an acetate-assisted mechanism with the carboxylate likely serving as an intramolecular base. The viability of acetate-assisted C-H activation at high valent palladium has important implications for the design and optimization of catalytic processes involving this transformation as a key step.

  DOI：

  10.1021/ja401557m