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化学学报 >

2023 , Vol. 81 >Issue 10: 1271 - 1279

DOI: https://doi.org/10.6023/A23060268

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 ,
  • 韩佳宏 ,
  • 潘一骁 ,
  • 郝伟 ,
  • 范青华
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  • 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
★庆祝《化学学报》创刊90周年.
†共同第一作者

收稿日期: 2023-06-02

  网络出版日期: 2023-07-11

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)

收起

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

  • Qingduan Meng ,
  • Jiahong Han ,
  • Yixiao Pan ,
  • Wei Hao ,
  • Qing-Hua Fan
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  • 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
★Dedicated to the 90th anniversary of Acta Chimica Sinica.
†These authors contributed equally to this work
*E-mail: ;

Received date: 2023-06-02

  Online published: 2023-07-11

Supported by

National Key R&D Program of China(2021YFA1500200); National Natural Science Foundation of China(92056108); National Natural Science Foundation of China(92256303)

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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

本文引用格式

孟庆端 , 韩佳宏 , 潘一骁 , 郝伟 , 范青华 . 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★[J]. 化学学报, 2023 , 81(10) : 1271 -1279 . DOI: 10.6023/A23060268

Abstract

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

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