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Carboxyl-containing covalent organic frameworks: Synthesis and application in the ruthenium-catalyzed ortho-benzylation

含羧基共价有机骨架的合成及其在钌催化邻位苄基 化反应中的应用

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Abstract

Imine-based covalent organic frameworks (COFs) with different functional groups have brought great application potentials in many fields, including heterogeneous catalysis. Herein, we report the synthesis of COFs containing carboxylic acid groups and their first application in the ruthenium-catalyzed synthesis of diarylmethane derivatives. Two new carboxyl-containing COFs (Tp-DAT and DHTA-DAT) have been prepared from 2,5-diaminoterephthalic acid and benzene-1,3,5-tricarbaldehyde derivatives with different numbers of hydroxy groups. Both Tp-DAT and DHTA-DAT COFs show high activity in the ruthenium-catalyzed ortho-C–H benzylation of 2-arylpyridines. Tp-DAT COF, which is fully linked by β-ketoenamine, has high stability, good yields and high chemoselectivity for ortho-benzylation and thus exhibits advantages in heterogeneous catalytic reactions.

摘要

含有不同官能团的亚胺基共价有机框架材料(COFs)在非均相催 化等领域具有很大的应用潜力. 本文合成了含羧基的COFs并将其首次 应用于钌催化合成二芳基甲烷衍生物. 以2,5-二氨基对苯二甲酸和含不 同羟基个数的苯-1,3,5-三醛衍生物为原料, 制备了两个新的含羧基 COFs (Tp-DAT和DHTA-DAT). Tp-DAT和DHTA-DAT COFs在钌催 化的2-芳基吡啶邻位苄基化反应中均表现出较高的活性. Tp-DAT COF 骨架完全由β-酮胺连接而成, 具有较高的稳定性, 使得邻位苄基化反应 获得更高的效率和化学选择性, 因此在非均相催化反应中更具优势.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21372211).

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Authors and Affiliations

  1. Department of Chemistry, University of Science and Technology of China, Hefei, 230026, China

    Nana Wang  (王娜娜), Hong Pan  (潘虹) & Guan-Wu Wang  (王官武)

  2. State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou, 730000, China

    Guan-Wu Wang  (王官武)

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  1. Nana Wang  (王娜娜)
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  2. Hong Pan  (潘虹)
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Contributions

Author contributions Wang GW supervised the project. Wang N conceived the idea of this work. Wang N and Pan H carried out the experiments and performed detailed physical characterization. Wang N and Wang GW wrote the manuscript. All authors contributed to the discussion of the results and revision of the manuscript.

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Correspondence to Guan-Wu Wang  (王官武).

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Conflict of interest The authors declare that they have no conflict of interest.

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Supplementary information Experimental details and supporting data are available in the online version of the paper.

Nana Wang is a PhD student in the group of Professor Guan-Wu Wang at the Department of Chemistry, University of Science and Technology of China. Her research mainly focuses on COF-based materials and their applications in heterogeneous catalytic reactions.

Guan-Wu Wang obtained his PhD degree from the Department of Chemistry, Lanzhou University in 1993. After working as a postdoc in China and abroad, he joined the Department of Chemistry, University of Science and Technology of China as a full professor. His current research interests include organic chemistry and materials science.

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Wang, N., Pan, H. & Wang, GW. Carboxyl-containing covalent organic frameworks: Synthesis and application in the ruthenium-catalyzed ortho-benzylation. Sci. China Mater. 66, 4689–4696 (2023). https://doi.org/10.1007/s40843-023-2625-7

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