化学学报 ›› 2023, Vol. 81 ›› Issue (10): 1271-1279.DOI: 10.6023/A23060268 上一篇    下一篇

所属专题: 庆祝《化学学报》创刊90周年合辑

研究论文

C1-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

孟庆端,a,b, 韩佳宏,a,b, 潘一骁a, 郝伟a,b,*(), 范青华a,b,*()   

  1. a 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
    b 中国科学院大学 北京 100049
  • 投稿日期:2023-06-02 发布日期:2023-07-06
  • 作者简介:
    庆祝《化学学报》创刊90周年.
    共同第一作者
  • 基金资助:
    国家重点研发计划(2021YFA1500200); 国家自然科学基金(92056108); 国家自然科学基金(92256303)

Asymmetric Synthesis of C1-Symmetric Chiral N-Heterocyclic Carbene (NHC) Ligands and Their Applications in Asymmetric Catalysis

Qingduan Meng,a,b, Jiahong Han,a,b, Yixiao Pana, Wei Haoa,b(), Qing-Hua Fana,b()   

  1. a Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190
    b University of Chinese Academy of Sciences, Beijing 100049
  • Received:2023-06-02 Published:2023-07-06
  • Contact: *E-mail: weihao@iccas.ac.cn; fanqh@iccas.ac.cn
  • About author:
    Dedicated to the 90th anniversary of Acta Chimica Sinica.
    These authors contributed equally to this work
  • Supported by:
    National Key R&D Program of China(2021YFA1500200); National Natural Science Foundation of China(92056108); National Natural Science Foundation of China(92256303)

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C1-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.

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

A class of C1-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.

Key words: chiral N-heterocyclic carbene ligand, asymmetric catalysis, Pd catalysis, Cu catalysis, reductive amination