[Pd-trans-C(Ph)=C(Cl)CH2NMe2(μ-Cl)]2 | 652133-62-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [Pd-trans-C(Ph)=C(Cl)CH2NMe2(μ-Cl)]2
• 英文别名: (Pd[κ1-C,κ1-N-C=(C6H5)C(Cl)CH2N(CH3)2](μ-Cl))2；(Pd[κ1-C,κ1-N-C=(C6H5)C(Cl)CH2NMe2](μ-Cl))2；2-chloro-N,N-dimethyl-3-phenylprop-2-en-1-amine;chloropalladium(1+)
• CAS: 652133-62-5；20492-75-5；652133-61-4
• 化学式: C₂₂H₂₆Cl₄N₂Pd₂
• 分子量: 673.114
• InChiKey: MUZIRMBVXJQCLC-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  6.42
• 重原子数：
  30
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  异氰酸叔丁酯 、 [Pd-trans-C(Ph)=C(Cl)CH2NMe2(μ-Cl)]2 以 氘代氯仿 为溶剂， 生成
  参考文献：
  名称：

  The retro-chloropalladation reaction of heterosubstituted alkynes

  摘要：

  The bridge-splitting reaction of dimeric palladacycles of the type {Pd[kappa(1)-C, kappa(1)-N-C(R) = C(Cl)CH2NMe2](mu-Cl)}(2) (R = Ph, Me, CH2CH2OH), derived from the chloropalladation of propargyl amines (RCdropCCH(2)NMe(2)), with pyridine (Py), triphenylphosphine (PPh3) and tert-butytisonitrile ((BuNC)-Bu-t) affords the monomeric compounds [PdC(R)=CCH2NMe2(Cl)L] (L = Py, PPh3, (BuNC)-Bu-t). These monomeric compounds are not stable in solution and undergo retro-chloropalladation reactions yielding the propargyl amines and [PdCl(L)-mu-Cl](2). This process is strongly dependent upon the nature of the incoming nucleophile (L), the R group on the metallated ligand and the temperature. The retro-halopalladation reaction is almost instantaneous in the case of the reaction of the bromo derivative [PdC(Ph)=C(Br)CH2NMe2-mu-Br](2) and pyridine at room temperature. These results can be rationalized in terms of the stability of the Pd-C bond of the intermediate monomeric compound [PdC(R)=C(X)CH2NMe2(X)L], that is directly related to the nature of its substituents R (Ph, Me and CH2CH2OH), of ligands which are both cis and trans to it (Py, (CNBu)-Bu-t, PPh3, Cl and Br) and the temperature. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0277-5387(03)00324-3
• 作为产物：
  描述：

  lithium tetrachloropalladate 、 N,N-二甲基-3-苯基-2-丙炔-1-胺 以 甲醇 为溶剂， 生成 [Pd-trans-C(Ph)=C(Cl)CH2NMe2(μ-Cl)]2
  参考文献：
  名称：

  Dupont, Jairton; Basso, Nara R.; Meneghetti, Mario R., Organometallics, 1997, vol. 16, p. 2386 - 2391

  摘要：

  DOI：
• 作为试剂：
  描述：

  4-溴苯乙酮 、 2-甲基-3-丁炔-2-醇 在 [Pd-trans-C(Ph)=C(Cl)CH2NMe2(μ-Cl)]2 四丁基醋酸铵 作用下， 以 N,N-二甲基乙酰胺 为溶剂， 反应 4.0h， 以45%的产率得到1-[4-(3-羟基-3-甲基丁-1-炔基)苯基]乙酮
  参考文献：
  名称：

  基于Palladacycle的简单高效的无铜催化体系，用于炔烃的芳构化

  摘要：

  衍生自3-（二甲氨基）-1的氯钯合成的palladacycle [Pd（k 2 -C，N -C（C 6 H 5）C（Cl）CH 2 NMe 2）（μ-Cl）] 2（1） -苯基-1-丙炔及其膦加合物[Pd（k 2 -C，N -C（C 6 H 5）C（Cl）CH 2 NMe 2）P（4-CF 3 C 6 H 4）3（Cl ）]（3）在相对温和的反应条件下促进溴代和碘代芳烃的炔基化反应。碘代芳烃和活化的溴代芳烃与末端炔烃的偶联可以在室温下进行。碘代芳烃的流失数最高可达到10 5，灭活的溴代芳烃的流失数最高可达到94，但温度更高（120°C）。选择性中毒实验（Hg，Collman和Crabtree试验）表明，可溶性Pd（0）物种是参与此C sp 2 –C sp偶联反应的最可能的催化活性物种。

  DOI：

  10.1002/adsc.200505310

文献信息

• Palladium(II)-Catalyzed Directed <i>anti-</i>Hydrochlorination of Unactivated Alkynes with HCl
  作者：Joseph Derosa、Annabelle L. Cantu、Mark N. Boulous、Miriam L. O’Duill、Joshua L. Turnbull、Zhen Liu、Daizy M. De La Torre、Keary M. Engle

  DOI：10.1021/jacs.7b00892

  日期：2017.4.12

  A regioselective anti-hydrochlorination of unactivated alkynes is reported. The reaction utilizes in situ generated HCl as the source of both the Cl- and H+ and is catalyzed by palladium(II) acetate, with loadings as low as 25 ppm. Removable picolinamide and 8-aminoquinoline bidentate directing groups are used to control the regioselectivity of the chloropalladation step and stabilize the resulting

  报道了未活化炔烃的区域选择性抗氢氯化作用。该反应利用原位生成的 HCl 作为 Cl- 和 H+ 的来源，并由乙酸钯 (II) 催化，负载量低至 25 ppm。可去除的吡啶甲酰胺和 8-氨基喹啉二齿导向基团用于控制氯钯化步骤的区域选择性，并稳定所得的链烯基钯 (II) 中间体，用于随后的原脱钯反应。该方法提供了以优异的产率和高区域选择性获得广泛的取代链烯基氯的途径。这种转化的产物通过 Stille 偶联成功衍生为多种三取代烯烃产物。进行了反应进程动力学分析，揭示了该催化过程的可能机制。
• Atropisomerism in palladacycles derived from the chloropalladation of heterosubstituted alkynes
  作者：Mara L. Zanini、Mario R. Meneghetti、Günter Ebeling、Paolo R. Livotto、Frank Rominger、Jairton Dupont

  DOI：10.1016/s0020-1693(03)00011-2

  日期：2003.7

  The chloropalladation of 2-substituted phenyl N,N-propargylamines, Y-2-C6H4C=CCH2NMe2 (1a, Y = H; 2a, Y = CF3; 3a, Y = OMe: 4a. Y = SMe and 5a, Y = NH2) affords palladacycles in different ratios of isomers (geometric and atropisomers). In solution, the parent alkyne (Y = H) and the CF3 substituted derivative generate a mixture of cisoid and transoid chloro-bridged dimer palladacycles of the type Pd[kappa(1)-C, kappa(1)-N-C=(Y-2-C6H4)C(cl)CH2NMe2](mu-Cl)}(2). Moreover, in the case in the case of Y = CF3 palladacyclic derivative each of the geometric isomers comprises a mixture of two diastereoisomers due to the restricted rotation of the C(vinyl)-C(aryl) sigma bond (atropisomers). Palladacycles 1a (Y = H) and 2a (Y = CF3) crystallize as the single transoid and cisoid-anti isomer. respectively. The OMe substituted alkyne yields a similar dimeric compound that crystallizes as a single cisoid-anti isomer. In solution this dimeric compound is in fast equilibrium with a monomeric pincer compound of the type Pd[kappa(1)-C, kappa(1)-N, kappa(1)-O-C=(MeO-2-C6H4)C(Cl)CH2NMe2](Cl) assisted through the weak coordination of the OMe group. Pincer palladacycles Pd[kappa(1)-C, kappa(1)-N, kappa(1)-Y-C=(Y-2-C6H4)C(Cl)CH2NMe2](Cl) (Y = SMe and NH2) were the sole products obtained in the chloropalladation of alkynes 4a and 5a. The bridge splitting reaction of the dimeric palladacycles 1b-3b with pyridine is highly selective, affording exclusively the corresponding monomeric compounds 1c-3c. The monomeric palladacycle 2d, which comprises a mixture of two atropisomers (2:1 ratio of antilsyn) was obtained from the reaction of 2b with 2-methylpyridine. Theoretical calculations indicated that the anti isomer of 2d is 5.42 kJ mol(-1) more stable than its syn isomer. (C) 2003 Elsevier Science B.V. All rights reserved.