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

doi:10.6023/A23060268

Acta Chimica Sinica ›› 2023, Vol. 81 ›› Issue (10): 1271-1279.DOI: 10.6023/A23060268 Previous Articles Next Articles

Special Issue: 庆祝《化学学报》创刊90周年合辑

Original article

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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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

Cite this article

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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Fig. & Tab. 8

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

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

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

Scheme 3. Synthesis of chiral diamines based on quinolinone

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

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

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

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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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★