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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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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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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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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DOI: https://doi.org/10.1038/s41557-021-00757-4
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