铜催化C—C/C—N键活化合成2,4,6-三芳基吡啶的研究
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摘要
研究了在无溶剂条件下,由铜盐催化的苄胺与查尔酮的C—N/C—C键活化串联反应,合成了一系列2,4,6-三芳基吡啶衍生物。重点考察了催化剂、反应温度和反应溶剂等因素对目标产物产率的影响,并通过核磁氢谱和碳谱对串联产物进行了结构鉴定。实验结果表明:在无溶剂情况下,三氟甲磺酸铜(Cu(OTf)_2)催化合成2,4,6-三芳基吡啶衍生物的产率高(60%～88%),该方法具有反应条件温和,原料易得和底物适用范围广等特点。
An efficient copper-catalyzed C—N/C—C bond cleavage of aromatic methylamines andα,β-unsaturated ketones was developed to construct 2,4,6-triarylpyridine derivatives under neat conditions.The effects of catalyst,reaction temperature and solvent were studied.The product structures were characterized by 1 H NMR and 13 C NMR.This simple fragment assembly strategy uses mild conditions and affords a broad range of 2,4,6-triarylpyridine derivatives in up to 60%-88% yield from simple and readily available starting materials.This method has the advantages of operational simplicity,simple and readily available starting materials and wide substrate scope.
An efficient copper-catalyzed C—N/C—C bond cleavage of aromatic methylamines andα,β-unsaturated ketones was developed to construct 2,4,6-triarylpyridine derivatives under neat conditions.The effects of catalyst,reaction temperature and solvent were studied.The product structures were characterized by 1 H NMR and 13 C NMR.This simple fragment assembly strategy uses mild conditions and affords a broad range of 2,4,6-triarylpyridine derivatives in up to 60%-88% yield from simple and readily available starting materials.This method has the advantages of operational simplicity,simple and readily available starting materials and wide substrate scope.
引文
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[4] Soumya T V, Ajmal C M, Bahulayan D. Synthesis of bioactive and fluorescent pyridine-triazole-coumarin peptidomimetics through sequential click-multicomponent reactions [J]. Bioorg Med Chem Lett, 2017, 27(3):450-455.
[5] Sasabe H, Kido J. Multifunctional Materials in High-Performance OLEDs: Challenges for Solid-State Lighting [J]. Chem Mater, 2011, 23 (3):621-630.
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[7] Hantzsch A. Condensationsprodukte aus Aldehydammoniak und ketonartigen Verbindungen[J]. Ber, 1881, 14:1637-1638.
[8] Huang H, Ji X, Wu W, et al. Copper-Catalyzed Formal C-N Bond Cleavage of Aromatic Methylamines: Assembly of Pyridine Derivatives[J]. J Org Chem, 2013, 78:3774-3782.
[9] Geng W, Zhang W, Hao W, et al. Cyclopentadiene-Phosphine/Palladium-Catalyzed Cleavage of C-N Bonds in Secondary Amines: Synthesis of Pyrrole and Indole Derivatives from Secondary Amines and Alkenyl or Aryl Dibromides [J]. J Am Chem Soc, 2012, 134 (50):20230-20233.