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  

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

作　　者：戴耀[1] 刘鹤松[2] 冯秀娟[1] 包明[1] 

机构地区：[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

出　　处：《催化学报》2011年第10期1617-1623,共7页

基　　金：国家自然科学基金(21073025)~~

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(1mol%)为催化剂前体、L5(6mol%)为配体、叔丁醇钠(1.4mmol)为碱、甲苯为溶剂时,溴代芳烃与仲胺的偶联反应在100oC下可顺利进行,最高分离收率达到95%.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）.

关 键 词：膦 氮-配体 钯催化 碳-氮键偶联反应 芳基溴代物 仲胺 

分 类 号：O643.32[理学—物理化学]