C_(1)-对称手性氮杂环卡宾(NHC)配体的不对称合成及其催化性能研究  

Asymmetric Synthesis of C_(1)-Symmetric Chiral N-Heterocyclic Carbene(NHC)Ligands and Their Applications in Asymmetric Catalysis

作　　者：孟庆端 韩佳宏 潘一骁 郝伟 范青华[1,2] Meng Qingduan;Han Jiahong;PanYixiao;Hao Wei;Fan Qing-Hua(Beijing National Laboratory for Molecular Sciences,CAS Key Laboratory of Molecular Recognition and Function,Institute of Chemistry,Chinese Academy of Sciences,Beijing 100190;University of Chinese Academy of Sciences,Beijing 100049)

机构地区：[1]中国科学院化学研究所、中国科学院分子识别与功能重点实验室、北京分子科学国家研究中心,北京100190 [2]中国科学院大学,北京100049

出　　处：《化学学报》2023年第10期1271-1279,共9页Acta Chimica Sinica

基　　金：国家重点研发计划(No.2021YFA1500200);国家自然科学基金(Nos.92056108,92256303)资助.

摘　　要：以喹啉醛与芳胺化合物的不对称还原胺化为关键步骤,设计合成了一类C_(1)-对称且兼具手性并环与大位阻N-取代基两种优势结构单元的手性氮杂环卡宾配体.进一步以钯催化的分子内α-芳基化反应和铜催化的功能化烯烃质子硼化反应为模型反应,详细研究了该类配体的结构与催化性能的关系,发现四氢喹啉骨架上的8-位取代基以及大位阻手性N-取代基均对提升配体的手性诱导能力具有重要作用.A class of C_(1)-symmetric chiral N-heterocyclic carbene(NHC)ligands,incorporating both chiral fused-ring and sterically hindered N-substituted groups,were designed and synthesized,with the asymmetric reductive amination of quinoline aldehyde with arylamine compounds as the key step.Subsequently,using palladium-catalyzed intramolecular α-arylation and copper-catalyzed protoboration of functionalization of alkenes as the model reactions,the relationship between the structure of these ligands and their catalytic performance was systematically investigated.It was found that the 8-substituted groups on the tetrahydroquinoline scaffold and the bulky chiral N-substituted groups played important roles in enhancing the chiral induction ability of the ligands.

关 键 词：手性氮杂环卡宾配体 不对称催化 钯催化 铜催化 还原胺化 

分 类 号：O621.251[理学—有机化学] O643.36[理学—化学]