催化学报

催化学报 ›› 2011, Vol. 32 ›› Issue (10): 1617-1623.DOI: 10.3724/SP.J.1088.2011.10617

• 研究论文 • 上一篇    下一篇

新型 P, N-配体的合成及其在钯催化碳-氮键偶联反应中的应用

戴耀 1, 刘鹤松 2,a, 冯秀娟 1,b, 包明 1   

  1. 1 大连理工大学精细化工国家重点实验室, 辽宁大连 116024; 2 吉林大学第一医院皮肤性病科, 吉林长春 130021
  • 收稿日期:2011-06-09 修回日期:2011-06-28 出版日期:2011-09-30 发布日期:2015-02-12

Preparation and Application of New P, N-Ligands for Palladium-Catalyzed C–N Bond Coupling Reaction

DAI Yao1, LIU Hesong2,a, FENG Xiujuan1,b, BAO Ming1   

  1. 1State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, Liaoning, China; 2Department of Dermatology and Venereology, The First Hospital of Jilin University, Changchun 130021, Jilin, China
  • Received:2011-06-09 Revised:2011-06-28 Online:2011-09-30 Published:2015-02-12

PDF

1661

被引次数

8

摘要： 以三苯基膦为母体骨架, 设计合成了在苯环上连有环状仲胺取代基的五种新型 P, N-配体 (L1~L5), 利用核磁共振谱 (1H, 13C, 31P)、红外光谱、高分辨质谱和 X 射线单晶衍射等对配体进行了表征, 并将它们应用于 Pd 催化的 C–N 键偶联反应中. 结果表明, 三 (2-吗啉基苯基) 膦 (L5) 与三 (二亚苄基丙酮) 二钯 (Pd2(dba)3) 组成的体系可有效催化芳基溴代物与仲胺的偶联反应, 当以 Pd2(dba)3 (1 mol%) 为催化剂前体、L5 (6 mol%) 为配体、叔丁醇钠 (1.4 mmol) 为碱、甲苯为溶剂时, 溴代芳烃与仲胺的偶联反应在 100 oC 下可顺利进行, 最高分离收率达到 95%.

关键词: 膦,氮-配体, 钯催化, 碳-氮键偶联反应, 芳基溴代物, 仲胺

Abstract: P,N-ligands (L1–L5) with cyclic secondary amine moieties linked to the benzene rings of triphenylphosphine were designed and synthesized for the palladium-catalyzed C–N bond coupling reactions. The structures of these new P,N-ligands were confirmed by 1H NMR, 13C NMR, 31P NMR, infrared, high resolution mass spectroscopy, and X-ray single crystal diffraction. The desired C–N bond coupling products were obtained in good to excellent yields (up to 95%) when the reactions of aryl bromides with secondary amines were performed under the optimized reaction conditions (Pd2(dba)3, 1 mol%; L5, 6 mol%; NaOtBu, 1.4 mmol; toluene, 2.5 ml; 100 oC).

Key words: P,N-ligand, palladium catalysis, C–N bond coupling, aryl bromide, secondary amine