[Pd₂(C,N-C₆H₄CH₂CMe₂NH₂-2)₂(μ-Cl)₂] | 871258-01-4

• 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-C₆H₄CH₂CMe₂NH₂-2)₂(μ-Cl)₂]
• 英文别名: [Pd(C,N-C₆H₄CH₂CMe₂NH₂)(μ-Cl)]₂；[Pd2(κ-C,N-C6H4CH2CMe2NH2-2)2(μ-Cl)2]；[Pd2(2-C6H4CH2CMe2NH2-κC,N)2(μ-Cl)2]；[Pd2((phentermine)(-1H))2(chloride)2]；chloropalladium(1+);2-methyl-1-phenylpropan-2-amine
• CAS: 871258-01-4
• 化学式: C₂₀H₂₈Cl₂N₂Pd₂
• 分子量: 580.202
• InChiKey: MIWAKUMBUXUVDD-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  4.91
• 重原子数：
  26
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 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：

  [Pd₂(C,N-C₆H₄CH₂CMe₂NH₂-2)₂(μ-Cl)₂] 以 二氯甲烷 、 丙酮 为溶剂， 反应 4.38h， 生成 [Pd{C,N-C(Ph)C(Me)C₆H₄CH₂CMe₂NH₂}(OTf)(CO)]
  参考文献：
  名称：

  炔烃/ CO顺序插入后八元内酰胺合成中钯（II）有机羰基中间体的室温分离

  摘要：

  的双核配合物[钯（C ∧ N）（μ-X）] 2（C ∧ N = C ^，Ñ -C（PH）= C（R'）ARCH 2 CR 2 NH 2 -2;氩= C 6 ħ 4，C 6 H 2（OMe）2 -4,5; R = H，Me; R'= Ph，CO 2 Me，Me; X = Cl，Br），是由于内部炔烃单插入Pd–邻pal的苯丁胺或高藜芦胺的C键在室温下与CO反应，得到中性单核有机羰基配合物[Pd（C∧N）X（CO）]。当与CO反应中TlOTf的存在下进行时，triflato配合物[钯（C ∧ N）（OTF）（CO）]获得。这些有机羰基配合物尽管在相互顺式位置含有CO和σ-烯基配体，但仍显示出出乎意料的稳定性，并且代表了CO插入Pd–C键的插入反应中的真实中间体。的确，它们在适当的条件下经历分解，表现为释放CO的分子，或由于C–N偶联过程而产生Pd（0）和相应的二氢-3-苯并偶氮酮。每种化合物的晶体结构已通过X射线衍射研究确定。

  DOI：

  10.1021/om301241n
• 作为产物：
  描述：

  palladium diacetate 、 盐酸苯丁胺 以 乙腈 为溶剂， 以75%的产率得到[Pd₂(C,N-C₆H₄CH₂CMe₂NH₂-2)₂(μ-Cl)₂]
  参考文献：
  名称：

  Regiospecific Functionalization of Pharmaceuticals and Other Biologically Active Molecules through Cyclopalladated Compounds. 2-Iodination of Phentermine and l-Tryptophan Methyl Ester

  摘要：

  Phentermine hydrochloride ((PhCH2CMe2NH3)Cl) or L-tryptophan methyl ester hydrochloride ([C8H6NCH2CH(CO2Me)NH3]Cl) reacts with Pd(OAc)(2) in a 1:1 molar ratio to give the cyclometalated complex [Pd-2(kappa(2)-C,N-C6H4CH2CMe2NH2-2)(2)(Y-Cl)(2)] (1) or (S,S)-[Pd-2{kappa(2)-C,N- C8H5NCH2CH(CO2Me)NH2-2}(2)(mu-Cl)(2)] (2), respectively. Reaction of 1 or 2 with iodine affords trans-[PdC](2)(NH2CMe2CH2C6H4I-2)(2)] (3) or trans-(S,S)-[PdCl2{NH2CH(CO2Me)CH2C8H5NI-2}(2)] (4), which further reacts with 1,10-phenanthroline to give [PdCl2(phen)] and the free amine 2-I-phentermine (5) or (S)-2-I-tryptophan methyl ester (6) (overall yields 44 and 51%, respectively, considering phentermine and L-tryptophan methyl ester as starting materials). The crystal structure of complex 3 has been determined by X-ray diffraction studies.

  DOI：

  10.1021/om0506522

文献信息

• 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
• Reactivity of Eight-Membered Palladacycles Arising from Monoinsertion of Alkynes into the Pd–C bond of Ortho-Palladated Phenethylamines toward Unsaturated Molecules. Synthesis of Dihydro-3-Benzazocinones, N⁷-amino Acids, N⁷-amino Esters, and 3-Benzazepines
  作者：María-José Oliva-Madrid、José-Antonio Garcı́a-López、Isabel Saura-Llamas、Delia Bautista、José Vicente

  DOI：10.1021/om4010059

  日期：2014.1.13

  From the reactions of isocyanides R3NC with some eight-membered palladacycles arising from the insertion of one molecule of alkyne into the Pd–C bond of the palladacycles derived from homoveratrylamine and phentermine it is possible to isolate three different types of mononuclear complexes containing (1) coordinated R3NC, (2) coordinated and inserted R3NC, or (3) an unprecedented η3-allyl ligand involving

  从异氰化物R 3 NC与一些八元的Palladacycles的反应中，该分子是将一分子炔插入衍生自高藜芦胺和芬特明的Palladacycles的Pd–C键中，从而可以分离出三种包含（ 1）协调- [R 3 NC，（2）和配位插入- [R 3 NC，或（3）一个前所未有的η 3-涉及烯酮亚胺部分的烯丙基配体。这些络合物在适当的条件下分解，以提供金属钯和相应的由C-N偶联过程产生的八元氮杂环。八元palladacycles与CO在MeOH中反应生成Pd（0）和氨基酯。DFT观察并研究了从富马酸酯到马来酸酯的单一异构化过程。当在T1TfO存在下与CO反应时，可获得N 7-氨基酸衍生物。该合成方法还可用于制备衍生自邻金属化的高藜芦胺或芬特明的N 5-氨基酸。最后，用K t处理芬特明衍生的一种八元帕拉达环在回流的甲苯中加入BuO，然后添加HTfO，得到Pd（0）和二氢-3-苯并ze庚鎓盐。每种化合物的晶体结构已通过X射线衍射研究确定。
• Insertion of benzyne into the Pd–C bond. Synthesis of unnatural amino acid derivatives by sequential insertion of benzyne and CO: 2,2′-functionalized biaryls containing alkylamino and carboxymethyl substituents. Isolation of stable carbopalladated-benzyne intermediates
  作者：José-Antonio García-López、María-José Oliva-Madrid、Isabel Saura-Llamas、Delia Bautista、José Vicente

  DOI：10.1039/c2cc32975a

  日期：——

  Reaction of ortho-palladated derivatives of phentermine and homoveratrylamine with benzyne allows the synthesis of enlarged eight-membered palladacycles resulting from the insertion of the aryne into the Pd–C bond, which subsequently react with CO, to render unnatural amino acid derivatives.

  芬特明和高藜芦胺的邻位钯化衍生物与苯炔反应，可以合成扩大的八元钯环，这是由于芳炔插入到 Pd-C 键中，随后与 CO 反应，生成非天然氨基酸衍生物。
• 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.