[PdBr2(NH2CH2CH2C6H3(OMe)2-3,4)2] | 1372870-51-3

• 英文名称: [PdBr2(NH2CH2CH2C6H3(OMe)2-3,4)2]
• CAS: 1372870-51-3
• 化学式: C₂₀H₃₀Br₂N₂O₄Pd
• 分子量: 628.697
• InChiKey: SGJQTQXZZLTVGI-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [PdBr2(NH2CH2CH2C6H3(OMe)2-3,4)2] 、 三苯基膦 以 二氯甲烷 为溶剂， 以89%的产率得到[PdBr2(NH2CH2CH2C6H3(OMe)2-3,4)(PPh3)]
  参考文献：
  名称：

  Ortho Palladation of the Phenethylamines of Biological Relevance l-Tyrosine Methyl Ester and Homoveratrylamine. Reactivity of the Palladacycles toward CO and Isocyanides. Synthesis of the Natural Alkaloid Corydaldine

  摘要：

  Palladacycles derived from L-tyrosine methyl ester, (S)-[Pd-2{C,N-C6H3CH2CH(CO2Me)NH2-2,(OH)-4}(2)(mu-Br)(2)] (1a-Br), and homoveratrylamine, [Pd-2{C,N-C6H2CH2CH2NH2-6, (OMe)(2)-3,4}(2)(mu-Br)(2)] (1b-Br), can be easily prepared in good yield by reacting Pd(OAc)(2), the corresponding ammonium triflate, and NaBr. Under the same conditions, the reaction of Pd(OAc)(2) with the free amine affords a low yield of the corresponding acetato complex 1a-OAc or 1b-OAc (the latter only detected in solution). In our hands, the previously reported palladation at the C2 position of homoveratrylamine with Pd(OAc)(2) is not observed. Instead, a complex mixture is obtained, mainly containing [Pd(OAc)(2){NH2CH2CH2C6H3(OMe)(2)-3,4}(2)] and minor amounts of 1b-OAc, which reacts with NaBr to afford a new mixture from which [PdBr2{NH2CH2CH2C6H3(OMe)(2)-3,4}(2)] can be isolated and characterized. These and other adducts can be isolated from Pd(OAc)(2), homoveratrylamine, and various ligands (PPh3 and Br-). 6-Bromohomoveratrylamine reacts with Pd(dba)(2) in the presence of tmeda to give the complex [Pd{C,N-C6H2CH2CH2NH2-6,(OMe)(2)-3,4}(tmeda)]Br. Reactions of complexes 1 with acetylacetonato or neutral (PR3) ligands give products resulting from substitution or bridge-splitting reactions. While La-Br reacts with XyNC (1:2 molar ratio) to give (S)-[Pd{C,N-C6H3CH2CH(CO2Me)NH2-2,(OH)-4}Br(CNXy)], 1b-Br gives [Pd{C,N-C (=NXy)-C6H2CH2CH2NH2-6, (OMe)(2)-3,4}Br(CNXy)]. (S)-7-Hydroxy-3-(methoxycarbonyl)-3,4-dihydroisoquinolin-1(2H)-one and 6,7-dimethoxy-3,4-dihydroisoquinolin-1(2H)-one (corydaldine) have been synthesized through the stoichiometric carbonylation of palladacycles 1a-Br and 1b-Br. The crystal structures of a solvento intermediate in the ortho-metalation reaction of the triflate derivative of L-tyrosine methyl ester and four other complexes have been determined by X-ray diffraction studies.

  DOI：

  10.1021/om300141b
• 作为产物：
  描述：

  3,4-二甲氧基苯乙胺 以 二氯甲烷 、 丙酮 为溶剂， 生成 [PdBr2(NH2CH2CH2C6H3(OMe)2-3,4)2]
  参考文献：
  名称：

  Ortho Palladation of the Phenethylamines of Biological Relevance l-Tyrosine Methyl Ester and Homoveratrylamine. Reactivity of the Palladacycles toward CO and Isocyanides. Synthesis of the Natural Alkaloid Corydaldine

  摘要：

  Palladacycles derived from L-tyrosine methyl ester, (S)-[Pd-2{C,N-C6H3CH2CH(CO2Me)NH2-2,(OH)-4}(2)(mu-Br)(2)] (1a-Br), and homoveratrylamine, [Pd-2{C,N-C6H2CH2CH2NH2-6, (OMe)(2)-3,4}(2)(mu-Br)(2)] (1b-Br), can be easily prepared in good yield by reacting Pd(OAc)(2), the corresponding ammonium triflate, and NaBr. Under the same conditions, the reaction of Pd(OAc)(2) with the free amine affords a low yield of the corresponding acetato complex 1a-OAc or 1b-OAc (the latter only detected in solution). In our hands, the previously reported palladation at the C2 position of homoveratrylamine with Pd(OAc)(2) is not observed. Instead, a complex mixture is obtained, mainly containing [Pd(OAc)(2){NH2CH2CH2C6H3(OMe)(2)-3,4}(2)] and minor amounts of 1b-OAc, which reacts with NaBr to afford a new mixture from which [PdBr2{NH2CH2CH2C6H3(OMe)(2)-3,4}(2)] can be isolated and characterized. These and other adducts can be isolated from Pd(OAc)(2), homoveratrylamine, and various ligands (PPh3 and Br-). 6-Bromohomoveratrylamine reacts with Pd(dba)(2) in the presence of tmeda to give the complex [Pd{C,N-C6H2CH2CH2NH2-6,(OMe)(2)-3,4}(tmeda)]Br. Reactions of complexes 1 with acetylacetonato or neutral (PR3) ligands give products resulting from substitution or bridge-splitting reactions. While La-Br reacts with XyNC (1:2 molar ratio) to give (S)-[Pd{C,N-C6H3CH2CH(CO2Me)NH2-2,(OH)-4}Br(CNXy)], 1b-Br gives [Pd{C,N-C (=NXy)-C6H2CH2CH2NH2-6, (OMe)(2)-3,4}Br(CNXy)]. (S)-7-Hydroxy-3-(methoxycarbonyl)-3,4-dihydroisoquinolin-1(2H)-one and 6,7-dimethoxy-3,4-dihydroisoquinolin-1(2H)-one (corydaldine) have been synthesized through the stoichiometric carbonylation of palladacycles 1a-Br and 1b-Br. The crystal structures of a solvento intermediate in the ortho-metalation reaction of the triflate derivative of L-tyrosine methyl ester and four other complexes have been determined by X-ray diffraction studies.

  DOI：

  10.1021/om300141b