(Z)-1-((ethoxycarbonyl)methyliden)-4,4-dimrthyl-2,3,4,5-tetrahydro-benzo[d]azepine | 1410788-48-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯氮卓类
• 英文名称: (Z)-1-((ethoxycarbonyl)methyliden)-4,4-dimrthyl-2,3,4,5-tetrahydro-benzo[d]azepine
• 英文别名: (Z)-ethyl 2-(4,4-dimethyl-2,3,4,5-tetrahydro-1H-benzo[d]azepin-1-ylidene)acetate；ethyl (2Z)-2-(2,2-dimethyl-3,4-dihydro-1H-3-benzazepin-5-ylidene)acetate
• CAS: 1410788-48-5
• 化学式: C₁₆H₂₁NO₂
• 分子量: 259.348
• InChiKey: JAEUFZUNHNHCJM-UKTHLTGXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  38.3
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  2,3-丁二烯酸乙酯 、 分特拉明 在 palladium diacetate 、 溶剂黄146 、 对苯醌 作用下， 反应 0.5h， 以13%的产率得到(Z)-1-((ethoxycarbonyl)methyliden)-4,4-dimrthyl-2,3,4,5-tetrahydro-benzo[d]azepine
  参考文献：
  名称：

  Catalytic C–H Activation of Phenylethylamines or Benzylamines and Their Annulation with Allenes

  摘要：

  Tetrahydro-3-benzazepines and tetrahydroiso-quinolines are synthesized in one,step from allenes and phenylethylamines or benzylamines,Mechanitically, it is assumed that activation of an aromatic ring with Pd(II) occurs, directed by the primary amine, leading to the formation of a palladacycltinto which'ari, allene then undergoes insertion. The resulting, pi-allyl intermediate cyclizes to the products by aniptramolecular allylic alkylation. The process is particularly useful with 2,3-butadienoates and amines having a quaternary carbon at the alpha-position.

  DOI：

  10.1021/jo501658s

文献信息

• 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.
• Catalytic C–H Activation of Phenylethylamines or Benzylamines and Their Annulation with Allenes
  作者：Aleix Rodríguez、Joan Albert、Xavier Ariza、Jordi Garcia、Jaume Granell、Jaume Farràs、Andrea La Mela、Ernesto Nicolás

  DOI：10.1021/jo501658s

  日期：2014.10.17

  Tetrahydro-3-benzazepines and tetrahydroiso-quinolines are synthesized in one,step from allenes and phenylethylamines or benzylamines,Mechanitically, it is assumed that activation of an aromatic ring with Pd(II) occurs, directed by the primary amine, leading to the formation of a palladacycltinto which'ari, allene then undergoes insertion. The resulting, pi-allyl intermediate cyclizes to the products by aniptramolecular allylic alkylation. The process is particularly useful with 2,3-butadienoates and amines having a quaternary carbon at the alpha-position.