[Pd(CH2-8-quinolyl)(OAc)]2 | 67773-32-4

• 英文名称: [Pd(CH2-8-quinolyl)(OAc)]2
• CAS: 67773-32-4
• 化学式: C₂₄H₂₂N₂O₄Pd₂
• 分子量: 615.29
• InChiKey: SVGIFXQQWZQZCB-UHFFFAOYSA-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

• 作为反应物：
  描述：

  [Pd(CH2-8-quinolyl)(OAc)]2 以 溶剂黄146 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.5h， 生成 喹啉-8-基甲基乙酸酯
  参考文献：
  名称：

  Aerobic C–H Acetoxylation of 8-Methylquinoline in Pd^II–Pyridinecarboxylic Acid Systems: Some Structure–Reactivity Relationships

  摘要：

  Catalytic oxidative C-H acetoxylation of 8-methylquinoline as a model substrate with O-2 as oxidant was performed using palladium(II) carboxylate catalysts derived from four different pyridinecarboxylic acids able to form palladium(II) chelates of different size. A comparison of the rates of the substrate C-H activation and the O-2 activation steps shows that the C-H activation step is rate-limiting, whereas the O-2 activation occurs at a much faster rate already at 20 degrees C. The chelate ring size and the chelate ring strain of the catalytically active species are proposed to be the key factors affecting the rate of the C-H activation.

  DOI：

  10.1021/om400618n
• 作为产物：
  描述：

  palladium diacetate 、 8-甲基喹啉 以 溶剂黄146 为溶剂， 反应 1.5h， 以85%的产率得到[Pd(CH2-8-quinolyl)(OAc)]2
  参考文献：
  名称：

  氧化还原偶涉及 NOxin 需氧 Pd 催化氧化 sp3-C-H 键：氧化和还原消除中 Pd-NO3-/NO2-相互作用的直接证据

  摘要：

  在氧化钯催化过程中，NaNO3 在 CH 键活化和瓦克氧化过程中用作常见氧化剂（例如 CuII 盐）的补充助催化剂。NaNO3 和 NaNO2（与空气或 O2）有助于带有 N 导向基团的底物的 sp3-CH 键乙酰氧基化。之前已经提出氧化还原对是有效的。本研究考察了 NOx 阴离子所起的作用。提供了 PdII 处 NOx 阴离子相互作用的证据。含有 NOx 阴离子的钯环配合物是 8-甲基喹啉乙酰氧基化的有效催化剂，有和没有外源性 NaNO3。在 PdII 处也注意到 8-甲基喹啉氧化成相应的羧酸。18O-标记研究表明来自硝酸盐的氧出现在乙酰氧基化产物中，它的转移只能通过 Pd 上的 18O 与配位乙酸盐配体的相互作用发生。硝化有机中间体在催化条件下形成，转化为乙酰氧基化产物，该过程在 (50 °C) 和无 Pd (110 °C) 下发生。已鉴定出具有催化能力的钯环二聚体中间体。顶空分析测量表明，将催化混合物从室温加热到

  DOI：

  10.1021/jacs.6b10853

文献信息

• Palladium-Catalyzed Intermolecular Oxidative Diazidation of Alkenes
  作者：Haihui Peng、Zheliang Yuan、Pinhong Chen、Guosheng Liu

  DOI：10.1002/cjoc.201600834

  日期：2017.6

  A palladium‐catalyzed oxidative vicinal diazidation of alkenes has been developed, in which TMSN3 was used as azide source. Both styrenes and unactivated alkenes are suitable for this reaction. And trans‐alkyldiazides were obtained as major products from cyclic alkenes with moderate to good diastereoselectivities. This reaction afforded an efficient way for the synthesis of useful 1,2‐diamines after

  已经开发了钯催化的烯烃氧化邻位叠氮化，其中TMSN 3被用作叠氮化物源。苯乙烯和未活化的烯烃均适用于该反应。而反式-alkyldiazides是从环烯烃主要产品有中到良好的非对映选择性获得。该反应提供了氢化后合成有用的1,2-二胺的有效方法。
• Palladium-Catalyzed C–H Bond Acetoxylation via Electrochemical Oxidation
  作者：Anuska Shrestha、Melissa Lee、Anna L. Dunn、Melanie S. Sanford

  DOI：10.1021/acs.orglett.7b03559

  日期：2018.1.5

  Here we describe the development of a method for the Pd-catalyzed electrochemical acetoxylation of C–H bonds. The oxidation step of the catalytic cycle is probed through cyclic voltammetry and bulk electrolysis studies of a preformed palladacycle of 8-methylquinoline. A catalytic system for C–H acetoxylation is then developed and optimized with respect to the cell configuration, rate of oxidation,

  在这里，我们描述了钯催化C–H键的电化学乙酰氧基化方法的发展。催化循环的氧化步骤通过循环伏安法和预先形成的8-甲基喹啉Palladacycle的本体电解研究进行探测。然后，针对电池的配置，氧化速率和对电极的化学性质，开发并优化了用于C–H乙酰氧基化的催化系统。然后，将这种转化应用于包含各种方向基团的底物以及C（sp 2）–H和C（sp 3）–H键的乙酰氧基化。
• Synthesis and structural study of [{Pd(CH₂C₉H₆N)}₂(µ-O₂CR)(µ-X)] complexes (R = Me or CF₃; X = hydroxide, amide or thiolate)
  作者：José Ruiz、Natalia Cutillas、Josefina Torregrosa、Gabriel García、Gregorio López、Penny A. Chaloner、Peter B. Hitchcock、Robin M. Harrison

  DOI：10.1039/dt9940002353

  日期：——

  The di-mu-carboxylato complexes [Pd(CH2C9H6N)(mu-O2CR)}2] (CH2C9H6N = 8-quinolylmethyl, R = Me or CF3) react in methanol with NaOH(aq) (1:1 molar ratio) to give the corresponding mixed hydroxocarboxylato-bridged complexes [Pd(CHC9H6N)}2(mu-OH)(mu-O2CR)] (R = Me 1 or CF3 2). The reactions of 1 or 2 with arylamines or thiols (1:1 molar ratio) yielded the corresponding amido- or thiolato-carboxylato complexes [Pd(CH2C9H6N)}2(mu-O2CMe)(mu-NHR)] (R = Ph 3, p-MeC6H4 4 or p-NO2C6H4 5) or [Pd(CHC9H6N)}2(mu-O2CR)(mu-SR')] (R = Me, R' = Et 6, Bu(t) 7, Ph 8 orp-MeC6H4 9; R = CF3, R' = Bu(t) 10). The H-1 NMR data indicate a cis arrangement of the CH2C9H6N ligands. The crystal structure of complex 10 has been determined. It confirms the cis relationship of the CH2C9H6N ligands. The co-ordination at each palladium atom is approximately square planar and the oxygen atoms of the trifluoroacetate ligands are trans to carbon. The Pd2(mu-OCOCF3)(mu-SBu(t)) core is quite bent with an angle of 55-degrees between the two palladium co-ordination planes.