[Pd₂(C,N-C₆H₄CH₂CH₂NH₂-2)₂(μ-Br)₂] | 187819-02-9

• 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: [Pd₂(C,N-C₆H₄CH₂CH₂NH₂-2)₂(μ-Br)₂]
• 英文别名: [Pd2(κ2(C,N)-C6H4-2-CH2CH2NH2)2(μ-Br)2]；[Pd2((phenethylamine)(-1H))2(bromide)2]；[Pd2(2-C6H4CH2CH2NH2-κC,N)2(μ-Br)2]；[Pd2(C,N-2-(phenyl)ethylamine(-1H))2(μ-Br)2]；Bromopalladium(1+);2-phenylethanamine
• CAS: 187819-02-9
• 化学式: C₁₆H₂₀Br₂N₂Pd₂
• 分子量: 612.996
• InChiKey: AUDSCYWMKJJPIS-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  3.66
• 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：

  3-甲基-1,2-丁二烯 、 [Pd₂(C,N-C₆H₄CH₂CH₂NH₂-2)₂(μ-Br)₂] 以 二氯甲烷 为溶剂， 反应 4.0h， 以82%的产率得到
  参考文献：
  名称：

  Insertion of Allenes into the Pd–C Bond of Ortho-Palladated Primary Arylamines of Biological Relevance: Phenethylamine, Phentermine, (l)-Phenylalanine Methyl Ester, and (l)-Tryptophan Methyl Ester. Synthesis of Tetrahydro-3-benzazepines and Their Salts

  摘要：

  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.

  DOI：

  10.1021/om300928j
• 作为产物：
  描述：

  diacetoxybis(phenethylamino)palladium 以 二氯甲烷 、 丙酮 、 乙腈 为溶剂， 生成 [Pd₂(C,N-C₆H₄CH₂CH₂NH₂-2)₂(μ-Br)₂]
  参考文献：
  名称：

  Orthometalation of Primary Amines. 4.¹ Orthopalladation of Primary Benzylamines and (2-Phenylethyl)amine

  摘要：

  By the refluxing of an acetonitrile solution of [Pd(OAc)(2)](3) and primary amines 4-XC(6)H(4)CH(2)NH(2) (F, Cl, NO2, OMe), 3,5-X(2)C(6)H(3)CH(2)NH(2) (X = OMe), or PhCH(2)CH(2)NH(2) (Pd:amine = 1:1) and subsequent addition of excess NaBr, the corresponding orthometalated complexes [Pd{C6H3(CH2NH2)-2,X-5}(mu-Br)](2), [Pd{C6H3(CH2NH2)-2,(OMe)(2)-4,6}(mu-Br)](2), or [Pd{C6H3(CH2NH2)-2}(mu-Br)](2) are obtained. Alternatively, the hydrochloride of 4-XC(6)H(4)CH(2)NH(2) (X = F, NO2) can also be used to prepare the corresponding [Pd{C6H3(CH2NH2)-2,X-5}(mu-Cl)](2) complexes. These results show that primary benzylamines can be orthometalated even if the substituents are electron-withdrawing groups and that 2-(phenyl)ethylamine can be orthometalated in spite of the six-membered ring that it forms. These reactions occur via intermediate complexes [Pd(OAc)(2)L(2)], which react with [Pd(OAc)(2)](3) to give the dimeric species [Pd(OAc)(mu-OAc)L](2) (L = amine), from which in turn the orthometalated complexes are formed. Each of these steps has been studied, and both types of intermediates have been isolated for all the amines. PPh(3) reacts with the orthometalated complexes to give the corresponding products of the bridge splitting. The crystal structures of [Pd(OAc)(mu-OAc)L](2) (L = 4-O2NC6H4CH2NH2) and [Pd{C6H4(CH2CH2NH2)-2}Br(PPh(3))] have been determined by X-ray diffraction.

  DOI：

  10.1021/om9609574

文献信息

• Insertion of One, Two, and Three Molecules of Alkyne into the Pd−C Bond of Ortho-palladated Primary and Secondary Arylalkylamines
  作者：José Vicente、Isabel Saura-Llamas、Juana Turpín、Delia Bautista、Carmen Ramírez de Arellano、Peter G. Jones

  DOI：10.1021/om9002895

  日期：2009.7.27

  (E)) react with RC≡CR (R = Et, Ph) to give [Pdκ2(C,N)-C(R)═C(R)C(R)═C(R)C6H3CH2NH2-2,X-5}Br] (X = Cl, R = Et (7a), Ph (7b); X = F, R = Et (8a), Ph (8b); X = NO2, R = Ph (9)) through a double insertion of the alkyne into the Pd−C bond. Complexes A and D react with PhC≡CCO2R in molar ratio 1:6−7 to afford a mixture of di-inserted head-to-tail and tail-to-tail isomers [Pdκ2(C,N)-C(R′)═C(R′′)C(Ph)═C(CO2

  的邻位金属化配合物[钯2 κ 2（C，N）-C 6 H ^ 4 CH 2 CH 2 NHMe-2} 2（μ-溴）2 ]（1）可通过一个回流1来制备：1混合物在乙腈中加入Pd（OAc）2和N-甲基苯乙胺，然后加入过量的NaBr。复杂1起反应以PPH 3，得到单核衍生物[钯κ 2（C ^，Ñ）-C 6 H ^ 4 CH 2 CH 2NHMe-2} Br（PPh 3）]（2）。阳离子络合物[钯κ 2（C ^，Ñ）-C 6 H ^ 4 CH 2 CH 2 NHMe-2}（PY）2 ] CLO 4（3）可通过反应而得到的1与AgClO 4和吡啶。先前报道的络合物[钯2 κ 2（C，N）-C 6 H ^ 4 CH 2 NHCH 2 PH-2} 2（μ-溴）2 ]（甲）反应与PhC≡CCO 2 R（R = ME等），得到monoinserted衍生物[钯2 κ 2（C ^，Ñ）-C（PH）= C（CO
• Eight-Membered Palladacycles Derived from the Insertion of Olefins into the Pd−C Bond of Ortho-Palladated Pharmaceuticals Phenethylamine and Phentermine. Synthesis of Stable Heck-Type Intermediates Containing Accessible β-Hydrogens and Its Use in the Synthesis of 2-Styrylphenethylamines, Tetrahydroisoquinolines, and Eight-Membered Cyclic Amidines
  作者：José Vicente、Isabel Saura-Llamas、José-Antonio García-López、Delia Bautista

  DOI：10.1021/om100738z

  日期：2010.10.11

  the product of its insertion into the Pd−C bond, [PdC,N-CH(R′)CH2C6H4CH2CR2NH2-2}(μ-X)]2 (olefin = CH2═CHR′; R = H, X = Br, R′ = C(O)Me (1a), CO2Et (1c); R = Me, X = Cl, R′ = C(O)Me (1b), CO2Et (1d)) and [PdC,N-CH(C5H8)CHC6H4(CH2CMe2NH2)-2}(μ-Cl)]2 (olefin = norbornene, C5H8; 1e) or (2) the decomposition products of 1, i.e., Pd(0) and the complexes containing the arylated olefin, trans-[PdX2(NH2CR2CH2C6H4CH═CHPh-2)2]

  衍生自苯乙胺和芬特明的邻位金属配合物，[Pd（C，N -C 6 H 4 CH 2 CR 2 NH 2 -2）（μ-X）] 2（R = H，X = Br（A）; R = Me，X = Cl（B）），与烯烃反应，得到（1）其插入Pd-C键的产物[Pd C，N -CH（R'）CH 2 C 6 H 4 CH 2 CR 2 NH 2 -2}（μ-X）] 2（烯烃= CH 2 = CHR'; R = H，X = Br的，R'= C（O）Me（1A），CO 2Et（1c）; R = Me，X = Cl，R'= C（O）Me（1b），CO 2 Et（1d））和[Pd C，N -CH（C 5 H 8）CHC 6 H 4（CH 2 CMe 2 NH 2）-2}（μ-Cl）] 2（烯烃=降冰片烯，C 5 H 8；1e）或（2）1的分解产物，即Pd（0）和含有芳基化烯烃的配合物，反式-[PdX 2（NH 2
• 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。
• 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.
• Orthometalation of Primary Amines. 4.¹ Orthopalladation of Primary Benzylamines and (2-Phenylethyl)amine
  作者：José Vicente、Isabel Saura-Llamas、Michael G. Palin、Peter G. Jones、M. Carmen Ramírez de Arellano

  DOI：10.1021/om9609574

  日期：1997.3.1

  By the refluxing of an acetonitrile solution of [Pd(OAc)(2)](3) and primary amines 4-XC(6)H(4)CH(2)NH(2) (F, Cl, NO2, OMe), 3,5-X(2)C(6)H(3)CH(2)NH(2) (X = OMe), or PhCH(2)CH(2)NH(2) (Pd:amine = 1:1) and subsequent addition of excess NaBr, the corresponding orthometalated complexes [PdC6H3(CH2NH2)-2,X-5}(mu-Br)](2), [PdC6H3(CH2NH2)-2,(OMe)(2)-4,6}(mu-Br)](2), or [PdC6H3(CH2NH2)-2}(mu-Br)](2) are obtained. Alternatively, the hydrochloride of 4-XC(6)H(4)CH(2)NH(2) (X = F, NO2) can also be used to prepare the corresponding [PdC6H3(CH2NH2)-2,X-5}(mu-Cl)](2) complexes. These results show that primary benzylamines can be orthometalated even if the substituents are electron-withdrawing groups and that 2-(phenyl)ethylamine can be orthometalated in spite of the six-membered ring that it forms. These reactions occur via intermediate complexes [Pd(OAc)(2)L(2)], which react with [Pd(OAc)(2)](3) to give the dimeric species [Pd(OAc)(mu-OAc)L](2) (L = amine), from which in turn the orthometalated complexes are formed. Each of these steps has been studied, and both types of intermediates have been isolated for all the amines. PPh(3) reacts with the orthometalated complexes to give the corresponding products of the bridge splitting. The crystal structures of [Pd(OAc)(mu-OAc)L](2) (L = 4-O2NC6H4CH2NH2) and [PdC6H4(CH2CH2NH2)-2}Br(PPh(3))] have been determined by X-ray diffraction.