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

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.