Cs_(2)CO_(3)辅助钯催化X—H(X=C、O、N、B)官能团化反应的理论计算研究  

Computational Study on Cs_(2)CO_(3)-Assisted Palladium-Catalyzed X—H(X=C,O,N,B)Functionalization Reactions

作　　者：白文己 石宇冰 母伟花[1] 李江平 于嘉玮 Wenji Bai;Yubing Shi;Weihua Mu;Jiangping Li;Jiawei Yu(Faculty of Chemistry and Chemical Engineering,Yunnan Normal University,Kunming 650500,China)

机构地区：[1]云南师范大学化学化工学院,昆明650500

出　　处：《化学进展》2022年第10期2283-2301,共19页Progress in Chemistry

基　　金：国家自然科学基金(No.21763033);云南省万人计划“青年拔尖人才”专项资助。

摘　　要：钯催化X—H(X=C、O、N、B)官能团化反应是重要的有机合成策略,能以芳基卤化物、烯类或炔类等小分子化合物为底物,以原子经济的方式构建C—C和C—X(X=O、N、B)键。其中,Cs_(2)CO_(3)辅助钯催化X—H(X=C、O、N、B)官能团化反应因具有反应性好、产率高、底物适用范围广等优点,成为近年来有机合成领域的关注热点之一,在构建含C—C和C—X键的多环天然产物骨架方面起着重要作用。采用DFT理论研究Cs_(2)CO_(3)辅助钯催化X—H(X=C、O、N、B)官能团化反应,能帮助人们从微观层面了解该类反应的实质,进而为设计新的实验合成路线提供启示。本文对近十年来Cs_(2)CO_(3)辅助钯催化X—H(X=C、O、N、B)官能团化反应的最新理论研究进展进行分类和总结,对反应的微观机理以及Cs_(2)CO_(3)在反应中的作用机制进行了深入探讨,并对该领域的现存问题和发展前景进行了总结与展望。Palladium-catalyzed X—H(X=C,O,N,B)functionalization reaction is an important organic synthesis strategy,which can build C—C and C—X(X=O,N,B)bonds in an atomically economical way by employing small molecules such as aryl halides,alkenes or alkynes as substrates.Due to its high yield,good reactivity and wide substrate compatibility,Cs_(2)CO_(3)-assisted palladium-catalyzed X—H(X=C,O,N,B)functionalization reaction has become one of the hot spots in the field of organic synthesis in recent years,and has played a crucial role in constructing C—C and C—X bonds in polycyclic natural product skeletons.Based on previous experimental results,density functional theory(DFT)has been employed to study the Cs_(2)CO_(3)-assisted palladium-catalyzed X—H(X=C,O,N,B)functionalization reaction in detail,so as to help people understand the essence of this type of reaction at microscopic level,and provide inspiration for designing new experimental synthetic routes.Herein,the latest density functional theory research results on Cs_(2)CO_(3)-assisted palladium-catalyzed X—H(X=C,O,N,B)functionalization reactions have been summarized,with corresponding computational results about microcosmic reaction mechanism and role of Cs_(2)CO_(3)additive emphasized.The present issues and prospects of future development in this field are also summarized and forecast in the end.

关 键 词：钯催化 X—H官能团化 Cs_(2)CO_(3) 反应机理 选择性 DFT 

分 类 号：O643.12[理学—物理化学]