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★

doi:10.6023/A23060268

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^,^*()

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 Pan^a, Wei Hao^a^,^b(), Qing-Hua Fan^a^,^b()

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)

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1. Supporting Information-A23060268.pdf(9321KB)

摘要/Abstract

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

引用此文

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.

Qingduan Meng, Jiahong Han, Yixiao Pan, Wei Hao, Qing-Hua Fan. Asymmetric Synthesis of C₁-Symmetric Chiral N-Heterocyclic Carbene (NHC) Ligands and Their Applications in Asymmetric Catalysis^★[J]. Acta Chimica Sinica, 2023, 81(10): 1271-1279.

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图/表 8

图式1. 代表性IMes型手性配体和C1-对称手性NHC配体的设计合成

Scheme 1. Representative IMes-type chiral ligands, design and synthesis of C1-symmetric chiral NHC ligands

表1. 钌催化还原胺化/不对称氢化串联反应合成手性二胺化合物a

Table 1. Synthesis of chiral diamine compounds via Ru-catalyzed reductive amination/asymmetric hydrogenation cascade reaction

图式2. 3-苯基取代四氢喹啉骨架的手性二胺合成

Scheme 2. Synthesis of chiral diamines with a 3-phenyl-substituted tetrahydroquinoline scaffold

图式3. 基于喹啉酮的手性二胺合成

Scheme 3. Synthesis of chiral diamines based on quinolinone

图式4. 8-芳基取代四氢喹啉骨架的手性二胺合成

Scheme 4. Synthesis of chiral diamines with an 8-aryl-substituted tetrahydroquinoline scaffold

表2. C1-对称手性NHC配体前体的不对称合成a

Table 2. Asymmetric synthesis of C1-symmetric chiral precursors of NHC ligands

表3. C1-对称NHC配体在α-芳基化反应中的应用a

Table 3. Application of C1-symmetric NHC ligands in α-arylation reaction

表4. C1-对称NHC配体在质子硼化反应中的应用a

Table 4. Application of C1-symmetric NHC ligands in protoboration reaction

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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^★

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

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