铜金属配合物在可见光下催化胺与芳香腈的偶联反应  

Coupling reaction of amines with aromatic nitriles catalyzed by copper complex under visible light

作　　者：张一品[1,2,3] 张金相 刘鲲[1,2,3] 王斌[1,2,3] 

机构地区：[1]天津师范大学化学学院,天津300387 [2]天津师范大学无机-有机杂化功能材料化学教育部重点实验室,天津300387 [3]天津师范大学天津市功能分子结构与性能重点实验室,天津300387

出　　处：《天津师范大学学报（自然科学版）》2017年第1期42-45,共4页Journal of Tianjin Normal University：Natural Science Edition

基　　金：国家自然科学基金资助项目(21102101,21172173)

摘　　要：为了寻求一种能够替代昂贵的铱催化剂(Ir(ppy)3)催化胺与芳香腈偶联反应的新型催化剂,以邻菲啰啉类配体、双(2-二苯基磷苯基)醚、四乙腈四氟硼酸铜等为底物人工合成一种光催化剂2,9-二丁基-1,10-邻菲啰啉双(2-二苯基磷苯基)醚一价铜配合物(Cu1),产率为70%.以对苯二腈(芳香腈)和1-苯基吡咯(胺类)为底物,筛选出最佳的Cu1催化剂用量(5.0μmol)、碱的种类(Na OAc)和反应时间(12 h).在此条件下,选用不同种类的胺和不同种类的带有拉电子取代基的芳香腈作为反应底物,以Cu1为光催化剂,成功合成了8种化合物,产率为68%~91%.这些结果表明Cu1确实可以取代Ir(ppy)3催化胺与芳香腈的偶联反应,得到同样的偶联产物.To get a new catalyst which can replace expensive Ir（ppy ）3 to catalyze the coupling reaction of amine and aromatic- nitrile, 2, 9-dibutyl-1, lO-phenanthroline （oxydi-2, 1-phenylene）bis （diphenylphosphine） monovalent copper complex （Cul） was synthesized from phenanthroline ligands, （oxydi-2, 1-phenylene）bis （diphenylphosphine） and [Cu （MeCN）4][BF4]. The yield was 70%. By using terephthalonitrile （aromatic nitrile） and 1-phenylpyn＇ole （amine） as substrates, the most favorable amount of catalyst （5.0 txmol）, type of base （NaOAc） and reaction time （12 h） were screened out. Under such conditions, different kinds of amines and electron-withdrawing groups of aromatic nitriles were taken as the reaction substrates and Cul was adopted as the photocatalyst, Eight compounds were successfully synthesized, and the yields were between 68% and 91%. These results confirmed that Cul can surely replace Ir（ppy）3 to catalyze the coupling reaction of amine and aromat- icnitrile and get the same coupling products.

关 键 词：铜金属配合物 光催化 胺 芳香腈 偶联反应 

分 类 号：O634[理学—高分子化学]