chloro [2-(2-aminoethyl)phenyl] palladium(II) dimer | 1323952-89-1

• 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: chloro [2-(2-aminoethyl)phenyl] palladium(II) dimer
• 英文别名: [Pd₂(C,N-C₆H₄CH₂CH₂NH₂-2)₂(μ-Cl)₂]；[Pd2(C,N-2-(phenyl)ethylamine(-1H))2(μ-Cl)2]；chloropalladium(1+);2-phenylethanamine
• CAS: 1323952-89-1
• 化学式: C₁₆H₂₀Cl₂N₂Pd₂
• 分子量: 524.094
• InChiKey: ZZOWFPYHHUZJSL-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  3.35
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  52
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  chloro [2-(2-aminoethyl)phenyl] palladium(II) dimer 在 potassium carbonate 作用下， 以 二氯甲烷 、 丙酮 、 甲苯 为溶剂， 反应 14.5h， 生成 吲哚啉
  参考文献：
  名称：

  NH 2键合的环钯缩合的1-苯丙氨酸与碱辅助的分子内C–N偶联反应成吲哚-2-羧酸

  摘要：

  对苯丙氨酸衍生的palladacycles的去质子化分子内胺化反应进行了研究，以突出在碳氮键形成之前碳酸盐辅助的NH活化的简便性。一个主要的抗衡离子效应导致了不同的途径，其中SPhos-Pd与碘，三氟甲磺酸根或三氟乙酸根阴离子的络合物是获得（S）-2-二氢吲哚羧酸衍生物的关键中间体。

  DOI：

  10.1021/acs.organomet.0c00030
• 作为产物：
  描述：

  2-苯乙胺 以 二氯甲烷 、 乙腈 为溶剂， 反应 6.25h， 生成 chloro [2-(2-aminoethyl)phenyl] palladium(II) dimer
  参考文献：
  名称：

  NH 2键合的环钯缩合的1-苯丙氨酸与碱辅助的分子内C–N偶联反应成吲哚-2-羧酸

  摘要：

  对苯丙氨酸衍生的palladacycles的去质子化分子内胺化反应进行了研究，以突出在碳氮键形成之前碳酸盐辅助的NH活化的简便性。一个主要的抗衡离子效应导致了不同的途径，其中SPhos-Pd与碘，三氟甲磺酸根或三氟乙酸根阴离子的络合物是获得（S）-2-二氢吲哚羧酸衍生物的关键中间体。

  DOI：

  10.1021/acs.organomet.0c00030

文献信息

• TRIARYL PHOSPHINE LIGANDS, PREPARATION METHOD THEREFOR, AND USE IN CATALYSING COUPLING REACTIONS
  申请人：DONGGUAN STEPHEN CATALYST CO., LTD.

  公开号：US20210147452A1

  公开（公告）日：2021-05-20

  Provided are triaryl phosphine ligands, as shown in general formulae Ia and Ib, or a mixture thereof, and a preparation method therefor. The invention addresses the deficiencies of biaryl phosphine ligands invented by Buchwald et al. Also provided are a triaryl phosphine coordinated palladium complex, a system composed of triaryl phosphine ligand and a palladium salt or complex, and a use of the triaryl phosphine coordinated palladium complex in catalysing organic reactions, in particular a use in catalysis of coupling reactions involving (pseudo)halogenated aromatic hydrocarbon as substrate.

  提供了三芳基膦配体，如一般式Ia和Ib所示，或其混合物，以及其制备方法。该发明解决了Buchwald等人发明的双芳基膦配体的不足之处。还提供了一种三芳基膦配体配合钯络合物，由三芳基膦配体和钯盐或络合物组成的体系，以及三芳基膦配体配合钯络合物在催化有机反应中的用途，特别是在催化涉及（伪）卤代芳香烃作为底物的偶联反应中的用途。
• A New Method for High-Yield Cyclopalladation of Primary and Secondary Amines. Atom-Efficient Open-to-Air Inexpensive Synthesis of Buchwald-Type Precatalysts
  作者：José Vicente、Isabel Saura-Llamas、María-José Oliva-Madrid、José-Antonio García-López、Delia Bautista

  DOI：10.1021/om200464s

  日期：2011.9.12

  A new method for high-yield cyclopalladation of primary and secondary amines involving the corresponding ammonium triflates, instead of the amines generally employed, is reported. The method is applied for the synthesis of Buchwald-type precatalysts [Pd(C,N-C6H4CH2CH(R′)NHR-2)X(phosphine)] that can be easily prepared by reaction of Pd(OAc)2, 1 equiv of the ammonium triflate [PhCH2CH(R′)NH2R]OTf, and

  据报道，涉及相应的三氟甲磺酸铵的伯胺和仲胺的高产环palpalladation的新方法，而不是通常使用的胺。该方法适用于布奇瓦尔德型预催化剂的合成[Pd（C，N -C 6 H 4 CH 2 CH（R'）NHR-2）X（膦）]，可以通过Pd（OAc）反应容易地制备）2，1当量的三氟甲磺酸铵[PhCH 2 CH（R'）NH 2 R] OTf和过量的NaX，然后处理所得的络合物[Pd 2（C，N -C 6 H 4 CH 2CH（R'）NHR-2）2（μ-X）2 ]与适当的膦。与Buchwald报道的合成方法相比，该新方法具有多个优点。
• 二联芳缩醛膦、它们的制备方法及在偶联反应中的用途
  申请人：东莞市均成高新材料有限公司

  公开号：CN110627831A

  公开（公告）日：2019-12-31

  本发明提供具有通式Ia和Ib的结构的带有缩醛基的二联芳单膦配体，或它们的混合物，和它们的制备方法。发明还描述了带有缩醛基的二联芳单膦配位的钯络合物。带有缩醛基的二联芳单膦配体与钯盐或络合物组成的体系、以及带有缩醛基的二联芳单膦配位的钯络合物在催化有机反应中的用途亦是本发明的一部分，特别是在催化涉及（拟）卤代芳烃为底物的偶联反应中的用途。
• Insertion of Allenes into the Pd–C Bond of Ortho-Palladated Primary Arylamines of Biological Relevance: Phenethylamine, Phentermine, (<scp>l</scp>)-Phenylalanine Methyl Ester, and (<scp>l</scp>)-Tryptophan Methyl Ester. Synthesis of Tetrahydro-3-benzazepines and Their Salts
  作者：José-Antonio García-López、Isabel Saura-Llamas、John E. McGrady、Delia Bautista、José Vicente

  DOI：10.1021/om300928j

  日期：2012.12.10

  The previously reported ortho-metalated complexes [Pd(C,N-ArCH2CRR'NH2-2)(mu-X)](2) derived from phenethylamine (Ar = C6H4, R = R' = H, X = Cl, Br), phentermine (Ar = C6H4, R = R' = Me, X = Cl), (L)-phenylalanine methyl ester (Ar = C6H4, R = H, R' = CO2Me, X = Cl, Br)), and (L)-tryptophan methyl ester (Ar = C8H5N, R = H, R' = CO2Me, X = Cl) react with various allenes to give (1) the corresponding eta(3)-allyl complexes derived from the insertion of one molecule of the allene into the Pd-C bond, the formation of which has been studied by DFT using a model complex, or (2) Pd(0) and the tetrahydro-3-benzazepinium salts, resulting from the decomposition of the above mentioned eta(3)-allyl complexes, containing an exocyclic double bond, which, subsequently, react with a base to afford the corresponding benzazepines. The regiochemistry of these decomposition reactions has been studied and compared wit:a that described for similar processes involving five-membered palladacycles. The crystal structures of the salts of some benzazepines and one isoquinoline, derived from a five-membered palladacycle, have been determined by X-ray diffraction studies.
• Norbornadiene as a Building Block for the Synthesis of Linked Benzazocinones and Benzazocinium Salts through Tetranuclear Carbopalladated Intermediates
  作者：José Antonio García-López、Roberto Frutos-Pedreño、Delia Bautista、Isabel Saura-Llamas、José Vicente

  DOI：10.1021/acs.organomet.6b00795

  日期：2017.1.23

  The six-membered C,N-palladacycle [Pd(C,N-C6H4CH2CMe2NH2-2)(mu-Cl)](2) (A) derived from phentermine reacts with norbornadiene to give a di- or tetranuclear complex arising from the double insertion of the same molecule of the strained alkene into one or two distinct Pd aryl bonds. The tetranuclear complex has been characterized by X-ray diffraction studies and exhibits a very unusual cisoid geometry in both the disposition of the C,N-chelate ligands and the position of the palladium centers. The newly formed Pd-alkyl bonds are still reactive toward the insertion of unsaturated molecules, and the tetranuclear complex reacts with CO or isocyanides to give double benzazocinones or benzazocinium salts with a cisoid geometry, after depalladation of the corresponding organometallic intermediates which have been isolated in some cases. When the related palladacycles derived from phenethylamine or N-methylphenethylamine are used as starting materials, polymeric compounds are obtained, from which double benzazocinones or benzazocinium salts with a transoid geometry are obtained after CO or RNC insertion and subsequent depalladation. The presence of substituents on the alpha-carbon atom of the chelated amine influences the regiochemistry of the double carbopalladation of the norbornadiene.