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Carbon monoxide enabling synergistic carbonylation and (hetero)aryl migration

Nature Catalysis (2024)Cite this article

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Abstract

The activation and transformation of carbon monoxide (CO), a versatile C1 feedstock, continues to attract substantial attention. Traditionally, researchers have focused on the development of catalytic systems to activate CO and then quench the generated acyl intermediate with nucleophiles to complete the carbonylative transformations. Here, non-classically, we unveil a visible-light-induced, carbonylation-triggered radical relay rearrangement reaction, in which the CO insertion step is a key element for functional group migration. The selective insertion of a carbonyl group into the newly generated carbon radical provides a bridge for (hetero)aryl group migration, and the positive feedback of group migration also enables the carbon radical to capture CO more efficiently. A series of 1,4-dicarbonyl compounds containing fluoroalkyl and heterocycles are synthesized successfully under mild conditions, and the conversion of the products to valuable heteroaromatic biaryls indicates the synthetic potential of this platform.

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Fig. 1: Background and introduction of carbonylation-triggered aryl/heteroaryl migration utilizing CO.
Fig. 2: Carbonylation-triggered migration.
Fig. 3: Expanding the radical scope and scale-up reaction.
Fig. 4: Modification of bioactive molecules.
Fig. 5: Mechanistic studies and derivatization of 1,4-diketone compounds.

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Data availability

The data supporting the findings of this study are available within the paper and its Supplementary Information or from the corresponding author upon request. The X-ray crystallographic coordinates for structure 6b reported in this article have been deposited at the Cambridge Crystallographic Data Centre (CCDC), under deposition number 2306994. These data can be obtained free of charge from the CCDC via www.ccdc.cam.ac.uk/data_request/cif.

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Acknowledgements

We thank the National Key R&D Program of China (2023YFA1507500) and the Chinese Academy of Sciences Dalian Institute of Chemical Physics (DICP) for financial support.

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Authors and Affiliations

  1. Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China

    Yuanrui Wang, Hefei Yang, Yan Zheng, Zhi-Peng Bao & Xiao-Feng Wu

  2. University of Chinese Academy of Sciences, Beijing, China

    Yuanrui Wang, Zhi-Peng Bao & Xiao-Feng Wu

  3. Leibniz-Institut für Katalyse e.V., Rostock, Germany

    Hefei Yang & Xiao-Feng Wu

  4. School of Chemistry and Chemical Engineering, Key Laboratory of Surface & Interface Science of Polymer Materials of Zhejiang Province, Zhejiang Sci-Tech University, Hangzhou, China

    Mingxia Hu, Jintao Zhu & Yanying Zhao

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Contributions

Y.W. designed and carried out most of the reactions and analysed the data. Y.W., H.Y., Y. Zheng and Z.-P.B. provided raw material support. M.H., J.Z. and Y. Zhao performed DFT calculations. X.-F.W designed and supervised the project. X.-F.W and Y.W. wrote and revised the paper.

Corresponding author

Correspondence to Xiao-Feng Wu.

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Supplementary information

Supplementary Information

Supplementary Methods, Figures 1–366, Tables 1 and 2, and References.

Supplementary Data 1

Crystallographic data of 6b.

Supplementary Data 2

DFT caculated energy profile.

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Wang, Y., Yang, H., Zheng, Y. et al. Carbon monoxide enabling synergistic carbonylation and (hetero)aryl migration. Nat Catal (2024). https://doi.org/10.1038/s41929-024-01204-6

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