[(Py3CH)PdIV(4'-tert-butyl-2'-deutero-5-fluoro-[1,1'-biphenyl]-2,2’-diyl)(Cl)][OAc] | 1431223-81-2

• 英文名称: [(Py3CH)PdIV(4'-tert-butyl-2'-deutero-5-fluoro-[1,1'-biphenyl]-2,2’-diyl)(Cl)][OAc]
• 英文别名: [(Py₃CH)Pd^IV(4'-tert-butyl-2'-deutero-5-fluoro-[1,1'-biphenyl]-2,2’-diyl)(Cl)][OAc]
• CAS: 1431223-81-2
• 化学式: C₂H₃O₂*C₃₂H₂₈ClFN₃Pd
• 分子量: 675.503
• InChiKey: NHYITUIERAUDHR-IYHCCICLSA-L

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  4-叔丁基苯胺 在 4-叔丁基吡啶 、 盐酸 、 bis-triphenylphosphine-palladium(II) chloride 、 正丁基锂 、 氘代盐酸 、 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 、 重水 为溶剂， 反应 34.0h， 生成 [(Py3CH)PdIV(4'-tert-butyl-2'-deutero-5-fluoro-[1,1'-biphenyl]-2,2’-diyl)(Cl)][OAc]
  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