氯化亚铜催化的2-吡啶酮C-N偶联反应的理论研究  

Theoretical investigations on the CuCl-catalysted C-N coupling reactions of 2-pyridinone

作　　者：陈艳[1] 李函伟 雍芳 潘金龙[3] 付豪 CHEN Yan;LI Han-wei;YONG Fang;PAN Jin-long;FU Hao(School of Information Engineering,Southwest University of Science and Technology,Mianyang 621010,China;College of Chemistry,Sichuan University,Chengdu 610065,China;Institute of Machinery Manufacturing Technology,China Academy of Engineering Physics,Mianyang 621900,China)

机构地区：[1]西南科技大学信息学院,四川绵阳621010 [2]四川大学化学学院,四川成都610064 [3]中国工程物理研究院机械制造工艺研究所,四川绵阳621900

出　　处：《化学研究与应用》2020年第5期764-770,共7页Chemical Research and Application

基　　金：校企合作项目(S18H321-Q);西南科技大学博士基金(14zx7121)资助;。

摘　　要：本文采用密度泛函(DFT)方法研究了氯化亚铜催化的2-吡啶酮与苯基碘鎓盐的C-N偶联反应,分别在气相和溶剂化条件下,优化了反应路径上的中间体(IM)和过渡态(TS)的结构,计算了各物种的能量和振动频率等。计算结果表明,反应是一个包含两步的催化循环过程:第一步是CuCl插入到底物N-H键中;第二步的2-吡啶酮中N原子与二-(4-叔丁基)苯基碘鎓盐中的芳环进行C-N偶联。结果表明,第二步能垒最高,为该反应的速控步,同时控制着该反应的收率。计算也表明,2-吡啶酮6号位上的取代基,通过影响过渡态中吡啶酮活性位上的电荷密度,来改变反应的能垒从而影响反应的动力学特性。Density functional theory(DFT)methodswere used to investigate theCuCl-catalyzedC?N coupling reaction.The calculations afford the geometrical optimizations of all the intermediates(IM)and transition states(TS),the energies and the vibration frequency of these intermediates and transition statesin the solution and the gas-phase,respectively.The results show that the reaction is a two-step catalytic cycle:1)the insertion of CuCl into the N-H bond of 2-pyridinone;2)the N atom of 2-pyridinone coupling to thephenyl moiety of bis(4-(tert-butyl)phenyl)iodonium triflate to form the C-N bond.It was found that the second reaction step possesses the largest energy barrier in the entire reaction,which indicates that this step is the rate-determining step(RDS)and accounts for the yield of final product.The calculation also indicates that the substituent group at the 6-position of the 2-pyridinone affects the charge accumulated at the active site of the substrate and therefore alters the kinetic properties of the entire reaction.

关 键 词：C-N偶联 2-吡啶酮 DFT 过渡态 机理 

分 类 号：O641.12[理学—物理化学]