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Hybrid cycloolefin ligands for palladium–olefin cooperative catalysis

Nature Synthesis volume 1, pages 180–187 (2022)Cite this article

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Abstract

The engineering of molecular catalysts in homogeneous catalysis enables new catalytic modes, which leads to efficient synthetic transformations. In this regard, the design of ligands for transition metal catalysis has played a major role. In transition metal catalysed reactions, olefins can serve as steering ligands by tuning the electronic and steric nature of the metal centre. Here we report unstrained olefin ligands that bear a P or S coordination site for use in the Pd-catalysed Catellani reaction. This olefin ligand shows a covalent catalytic function and enables an efficient ipso,ortho-difunctionalization of iodoarenes. Mechanistic analysis reveals a reversible covalent bonding between the substrate and the cycloolefin unit of the ligand, which forms key organopalladium intermediates to enable a new reactivity. Our results demonstrate a design concept that employs hybrid cycloolefin ligands as a covalent catalytic module, which opens up possibilities for further cooperative catalysis with other transition metal–olefin hybrids.

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Fig. 1: Olefin ligands and co-catalysts.
Fig. 2: Hybrid olefin ligands for Pd–olefin cooperative catalysis.
Fig. 3: Synthetic utility of the Pd–L19 catalytic system.
Fig. 4: Mechanism of the Pd–olefin cooperative catalysis with L4.

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Data availability

The data supporting the findings of this study are available within the paper and its Supplementary Information. Crystallographic data for the structures reported in this Article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 2060007 (9) and 2060009 (11). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/.

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Acknowledgements

Financial support was provided by the National Natural Science Foundation of China (grant number 21822304 to L.J.). M.-T. Zhang is acknowledged for insightful discussions. We thank F.-Y. Wang for performing a control experiment with substrate 1n and X. Xu for repeating the synthesis of complexes 9 and 11. The technological platform of CBMS is acknowledged for providing instrumentation.

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Authors and Affiliations

  1. Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua University, Beijing, China

    Ya-Xin Zheng & Lei Jiao

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  1. Ya-Xin Zheng
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Contributions

L.J. and Y.-X.Z. conceived the work and designed the experiments. Y.-X.Z. performed the laboratory experiments. L.J. and Y.-X.Z. analysed the data and co-wrote the manuscript.

Corresponding author

Correspondence to Lei Jiao.

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The authors declare no competing interests.

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Peer review information

Nature Synthesis thanks M. Ángeles Fernández-Ibáñez and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Thomas West was the primary editor on this article and managed its editorial process and peer review in collaboration with the rest of the editorial team.

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Supplementary information

Supplementary Information

Detailed experimental procedures and characterization data.

Supplementary Data 1

Crystallographic data of complex 9 (CCDC 2060007).

Supplementary Data 2

Structure factors for crystallographic complex 9 (CCDC 2060007).

Supplementary Data 3

Crystallographic data of complex 11 (CCDC 2060009).

Supplementary Data 4

Structure factors for crystallographic complex 11 (CCDC 2060009).

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Zheng, YX., Jiao, L. Hybrid cycloolefin ligands for palladium–olefin cooperative catalysis. Nat Synth 1, 180–187 (2022). https://doi.org/10.1038/s44160-021-00019-8

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