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Orthogonal cross-coupling through intermolecular metathesis of unstrained C(aryl)–C(aryl) single bonds

Nature Chemistry volume 13, pages 836–842 (2021)Cite this article

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Abstract

While metathesis reactions involving carbon–carbon double bonds, namely olefin metathesis, have been well established with broad utility in organic synthesis and materials science, direct metathesis of kinetically less accessible C–C single bonds is extremely rare. Here we report a ruthenium-catalysed reversible C–C single-bond metathesis reaction that allows redox- and pH-neutral biaryl synthesis. Assisted by directing groups, unstrained homo-biaryl compounds undergo aryl exchanges to generate cross-biaryl products, catalysed by a well-defined air-stable ruthenium(II) complex. Functional groups reactive under typical cross-coupling reactions, such as halogen, silyl and boronate moieties, are compatible under the metathesis conditions. Mechanistic studies disclose an intriguing ‘olefin-metathesis-like’ pathway that involves an unexpected heptacoordinated, 18-electron closed-shell intermediate. The distinct reaction mode discovered here is expected to inspire the development of more general C–C single-bond metathesis and orthogonal cross-coupling reactions.

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Fig. 1: Metathesis reactions of carbon−carbon double and single bonds.
Fig. 2: Exploration of a Ru-catalysed biaryl metathesis reaction.
Fig. 3: Preliminary mechanistic study.
Fig. 4: Further exploration of the reaction scope and limitation.

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Data availability

The data supporting the findings of this study are available within the paper and its Supplementary Information.

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Acknowledgements

We thank the University of Chicago and the NIH (2R01GM109054, G.D.) for research support. We are grateful for the support of the Research Computing Center at the University of Chicago for assistance with the calculations carried out in this work. P. Liu from the University of Pittsburgh is acknowledged for DFT advice.

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Author notes

  1. These authors contributed equally: Jun Zhu, Rui Zhang.

Authors and Affiliations

  1. Department of Chemistry, University of Chicago, Chicago, IL, USA

    Jun Zhu, Rui Zhang & Guangbin Dong

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  1. Jun Zhu
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  2. Rui Zhang
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  3. Guangbin Dong
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Contributions

J.Z. and G.D. conceived and designed the experiments. J.Z. performed experiments. R.Z. performed additional experiments and the DFT calculations. J.Z., R.Z. and G.D. co-wrote the manuscript.

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Correspondence to Guangbin Dong.

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Supplementary information

Supplementary Information

Procedural details, synthesis and characterization data, mechanistic experimental details, NMR spectra, X-ray crystallographic data, DFT calculation details, Cartesian coordinates of DFT structures, Supplementary Tables 2.1 and 8.1, Figs. 2.1 and 6.1, and Schemes 9.1–9.4.

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Zhu, J., Zhang, R. & Dong, G. Orthogonal cross-coupling through intermolecular metathesis of unstrained C(aryl)–C(aryl) single bonds. Nat. Chem. 13, 836–842 (2021). https://doi.org/10.1038/s41557-021-00757-4

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