[Pd(κ2C,O-C6H4NHC(O)NH(C6H4Me-4)-2)(N,N,N',N'-tetramethylethylenediamine)](triflate) | 868158-45-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: [Pd(κ2C,O-C6H4NHC(O)NH(C6H4Me-4)-2)(N,N,N',N'-tetramethylethylenediamine)](triflate)
• 英文别名: [Pd(κC,O-C6H4NHC(O)NH(C6H4Me-4)-2)(tmeda)]OTf
• CAS: 868158-45-6
• 化学式: CF₃O₃S*C₂₀H₂₉N₄OPd
• 分子量: 596.967
• InChiKey: MBIBISWMFBIILQ-UHFFFAOYSA-M

计算性质

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

反应信息

• 作为反应物：
  描述：

  [Pd(κ2C,O-C6H4NHC(O)NH(C6H4Me-4)-2)(N,N,N',N'-tetramethylethylenediamine)](triflate) 、 苯丙炔酸甲酯 以 二氯甲烷 为溶剂， 以86%的产率得到[Pd(κ2C,N-C(CO2Me)=C(Ph)C6H4NHC(O)NH(C6H4Me-4)-2)(tmeda)]OTf
  参考文献：
  名称：

  Synthesis and Reactivity of Ortho-Palladated Arylureas. Synthesis and Catalytic Activity of a C,N,C Pincer Complex. Stoichiometric Syntheses of Some N-Heterocycles

  摘要：

  1-(2-lodophenyl)-3-p-tolylurea (1) reacts with Pd(dba)(2) ([Pd-2(dba)(3)]-dba; dba = dibenzylideneacetone) in the presence of the appropriate ligands to give the ortho-palladated arylureas [Pd{C6H4NHC(O)NHTo-2}IL2] (To = C6H4Me-4; L-2 = tbubpy (4,4'-di-tert-butyl-2,2'-bipyridine) (2a), tmeda (N,N,N ',N '-tetramethylethylenediamine) (2b); L = PPh3 (2c)). Reaction of 2b with Tl(TfO) TfO = triflate, CF3SO3) results in the formation of cyclopalladated [Pd{kappa C-2,O- C6H4NHC(O)NHTo-2}(tmeda)]OTf (3b). The latter reacts with PPh3 to yield [Pd{C6H4NHC-(O)NHTo-2}(tmeda)(PPh3)]OTf (4b). Treatment of 2b with CO gives the corresponding acyl derivative [Pd{C(O)C6H4NHC(O)NHTo-2}I(tmeda)] (5b). If Tl(TfO) is added after the bubbling of CO, the C,N coupling product 3-p-tolyl-1H-quinazoline-2,4-dione (6) is formed. Complex 5b reacts with XyNC (Xy = 2,6-dimethylphenyl) to yield trans- [Pd{C(O)C6H4NHC-(O)NHTo-2}I(CNXy)(2)] (7). Both 5b and 7 decompose in solution to give 6. Complex 2b reacts with isocyanides to give the iminoacyl derivatives trans-[Pd{C(=NR)C6H4NHC(O)NHTo-2}I(CNR)2] (R = Xy (8x), Bu-t (8t)). The complex 8x gives the C,N coupling product 4-(xylylimino)-3-p-tolyl-3,4-dihydro-1H-quinazolin-2-one (9) after treatment with TlOTf 8x also reacts with bases (K2CO3 and Tl2CO3) to yield the iminoacyl amido carbene C,N,C pincer palladium complex [Pd{kappa C-3,N,C-C(=NXy)C6H4NC(O)NToC(NHXy)-2}(CNXy)] (10); this complex is an active precatalyst in Heck and Suzuki reactions. The reaction of 2b with R'C equivalent to CR" and TIOTf gives [Pd{kappa C-2,N-CR'=CR"C6H4NHC(O)NHTo-2}(tmeda)]OTf (R' = R" = Et (11be), CO2Me (11bm), Ph (11bp); R' = Ph, R" = CO2Me (11bq)). These complexes decompose in solution, and in the case of 11bp, 2,3-diphenylindole-l-carboxylic acid p-tolylamide (12p) was isolated. 11bq reacts with PPh3 to give 3-phenyl-1H-indole-2carboxylic acid methyl ester (13q). 11bp and 11bq decompose in the presence of CO to yield 3,4-diphenyl-2-quinolone (14po) and 2-oxo-4-phenyl-1,2-dihydroquinoline-3-carboxylic acid methyl ester (14qo), respectively. Similarly, when 11bq is reacted with XyNC, the C,N coupling compound 2-xylyl-4-phenyl-1,2-dihydroquinoline-3-carboxylic acid methyl ester (14qnx) is formed. The crystal and molecular structures of 3b, 10-0.5CDCl(3), 11bp-OEt2, 11bq, and 14po have been determined.

  DOI：

  10.1021/om050451y
• 作为产物：
  描述：

  [Pd(C6H4NHC(O)NH(C6H4Me-4)-2)I(N,N,N',N'-tetramethylethylenediamine)] 、 三氟甲磺酸铊 以 丙酮 为溶剂， 以70%的产率得到[Pd(κ2C,O-C6H4NHC(O)NH(C6H4Me-4)-2)(N,N,N',N'-tetramethylethylenediamine)](triflate)
  参考文献：
  名称：

  Synthesis and Reactivity of Ortho-Palladated Arylureas. Synthesis and Catalytic Activity of a C,N,C Pincer Complex. Stoichiometric Syntheses of Some N-Heterocycles

  摘要：

  1-(2-lodophenyl)-3-p-tolylurea (1) reacts with Pd(dba)(2) ([Pd-2(dba)(3)]-dba; dba = dibenzylideneacetone) in the presence of the appropriate ligands to give the ortho-palladated arylureas [Pd{C6H4NHC(O)NHTo-2}IL2] (To = C6H4Me-4; L-2 = tbubpy (4,4'-di-tert-butyl-2,2'-bipyridine) (2a), tmeda (N,N,N ',N '-tetramethylethylenediamine) (2b); L = PPh3 (2c)). Reaction of 2b with Tl(TfO) TfO = triflate, CF3SO3) results in the formation of cyclopalladated [Pd{kappa C-2,O- C6H4NHC(O)NHTo-2}(tmeda)]OTf (3b). The latter reacts with PPh3 to yield [Pd{C6H4NHC-(O)NHTo-2}(tmeda)(PPh3)]OTf (4b). Treatment of 2b with CO gives the corresponding acyl derivative [Pd{C(O)C6H4NHC(O)NHTo-2}I(tmeda)] (5b). If Tl(TfO) is added after the bubbling of CO, the C,N coupling product 3-p-tolyl-1H-quinazoline-2,4-dione (6) is formed. Complex 5b reacts with XyNC (Xy = 2,6-dimethylphenyl) to yield trans- [Pd{C(O)C6H4NHC-(O)NHTo-2}I(CNXy)(2)] (7). Both 5b and 7 decompose in solution to give 6. Complex 2b reacts with isocyanides to give the iminoacyl derivatives trans-[Pd{C(=NR)C6H4NHC(O)NHTo-2}I(CNR)2] (R = Xy (8x), Bu-t (8t)). The complex 8x gives the C,N coupling product 4-(xylylimino)-3-p-tolyl-3,4-dihydro-1H-quinazolin-2-one (9) after treatment with TlOTf 8x also reacts with bases (K2CO3 and Tl2CO3) to yield the iminoacyl amido carbene C,N,C pincer palladium complex [Pd{kappa C-3,N,C-C(=NXy)C6H4NC(O)NToC(NHXy)-2}(CNXy)] (10); this complex is an active precatalyst in Heck and Suzuki reactions. The reaction of 2b with R'C equivalent to CR" and TIOTf gives [Pd{kappa C-2,N-CR'=CR"C6H4NHC(O)NHTo-2}(tmeda)]OTf (R' = R" = Et (11be), CO2Me (11bm), Ph (11bp); R' = Ph, R" = CO2Me (11bq)). These complexes decompose in solution, and in the case of 11bp, 2,3-diphenylindole-l-carboxylic acid p-tolylamide (12p) was isolated. 11bq reacts with PPh3 to give 3-phenyl-1H-indole-2carboxylic acid methyl ester (13q). 11bp and 11bq decompose in the presence of CO to yield 3,4-diphenyl-2-quinolone (14po) and 2-oxo-4-phenyl-1,2-dihydroquinoline-3-carboxylic acid methyl ester (14qo), respectively. Similarly, when 11bq is reacted with XyNC, the C,N coupling compound 2-xylyl-4-phenyl-1,2-dihydroquinoline-3-carboxylic acid methyl ester (14qnx) is formed. The crystal and molecular structures of 3b, 10-0.5CDCl(3), 11bp-OEt2, 11bq, and 14po have been determined.

  DOI：

  10.1021/om050451y