羧基亚胺配体促进钯催化中药活性成分噻吩类化合物的C-H活化研究  

Study on carboxylic imine ligands applications for C-H activation of thiophene compounds from Traditional Chinese medicine active ingredients

作　　者：姚云[1] 兰小兵[1] 何小溪[1] 欧阳嘉盛 李艳芳[1] 申东升[1] 

机构地区：[1]广东药学院医药化工学院,广东中山528458

出　　处：《广东药学院学报》2015年第6期720-726,共7页Academic Journal of Guangdong College of Pharmacy

基　　金：国家自然科学基金项目(21004014)

摘　　要：目的通过羧基亚胺配体促进钯催化的C-H活化,得到一系列中药活性成分芳基噻吩类和芳基苯并噻吩类化合物。方法设计合成了3种羧基亚胺配体（L1~L3）,并应用于噻吩类化合物的C-H活化,筛选催化反应各因素得到较优条件,在较优条件下进行催化反应,分离纯化得目标产物。结果催化反应的最优条件：以1%（摩尔分数）的Pd Cl2和2%（摩尔分数）的配体作催化剂,N,N-二甲基乙酰胺为溶剂,K2CO3为碱,反应温度为130℃,反应时间为8 h,在空气中直接反应;3种配体中,L2的催化效果最好;以L2为配体进行了一系列催化反应,得到了12个芳基噻吩类和芳基苯并噻吩类化合物。结论本文设计合成的羧基亚胺配体对钯催化的C-H活化有明显的促进作用,其中对有吸电子基团的溴苯类底物活性较高。本研究对噻吩类中药活性成分的全合成、半合成或者结构修饰具有一定的参考价值。Objective To get the aryl thiophene and aromatic benzene thiophene compounds by carboxylic imine ligands applications for C-H activation of thiophene compounds from Traditional Chinese medicine active ingredients. Methods Three kinds of carboxylic imine ligands（ L1- L3） was designed and synthesized,and the carboxylic imine ligands were applied to C-H activation of thiophene compounds. The optimal conditions were screened to get the target products by separating and purifying. Results The optimal conditions were as follows： Pd Cl2（ 1%）,L（ 2%）,θ（ 130 ℃）,t（ 8 h） in the air. The results showed that L2 was the best in the three kinds of carboxylic imine ligands. A series of catalytic reactions with L2 ligands were performed,and twelve aryl thiophene and aromatic benzene thiophene compounds were obtained.Conclusion The use of carboxylic imine ligands has promotion for C-H activation by palladium catalytic,and the electron-withdrawing replaced bromobenzene has higher activity. The study has a certain reference value for synthetic,semi-synthetic or structure modification of Traditional Chinese medicine active ingredients.

关 键 词：羧基亚胺 C-H活化反应 中药活性成分 噻吩类化合物 

分 类 号：O626.12[理学—有机化学]