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Versatile and robust C–C activation by chelation-assisted manganese catalysis

Abstract

C–H activation has been recognized as an increasingly viable tool in molecular sciences, but organometallic C–C activation is scarce, and limited to precious and toxic metal catalysts. Herein, we disclose versatile C–C activations by a robust base-metal catalyst in water. Thus, an inexpensive manganese(i) catalyst enabled C–C functionalizations with excellent levels of chemo- and position-selectivities, setting the stage for versatile C–C allylations, C–C alkenylations and C–C alkylations in water. The manganese(i) catalyst outperformed commonly used copper, iron, palladium, rhodium and ruthenium complexes, and the C–C activations occurred on steroid and amino acid motifs. Detailed kinetic and computational studies provided strong support for a kinetically relevant C–C manganesation.

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Fig. 1: Manganese-catalysed C–C activation.
Fig. 2: Substitution pattern effect towards effective C–C cleavage.
Fig. 3: Robustness of the C–C activation.
Fig. 4: Versatility of the C–C alkylation.
Fig. 5: Position-selective manganese(i)-catalysed C–C activation highlighting unique benefits over C–H activation.
Fig. 6: Key mechanistic findings of C–C activation in water.
Fig. 7: Detailed spectroscopic, spectrometric and kinetic analysis of the manganese(i)-catalysed C–C activation.
Fig. 8: Computational density functional theory (DFT) studies, rationalizing the C–C activation mode of action.

Data availability

The X-ray crystallographic coordinates for the structure of compound C’ have been deposited at the Cambridge Crystallographic Data Centre (CCDC), under deposition number 1871580. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. All data is also available from the authors upon reasonable request.

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Acknowledgements

Generous support by the DFG (SPP 1807), the CSC (fellowship to H.W.), the KEF (fellowship to I.C.) and the Onassis Foundation (fellowship to N.K.) is gratefully acknowledged. We also thank C. Golz (Göttingen University) for the X-ray diffraction analysis.

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Authors and Affiliations

Authors

Contributions

H.W. developed the manganese-catalysed C–C activation. H.W., I.C. and N.K. identified the substrate scope. H.W., I.C. and T.R. conducted the mechanistic investigations. T.R. performed the computational studies. L.A. conceived and supervised the project. L.A. prepared the manuscript.

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Correspondence to Lutz Ackermann.

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Supplementary information

Supplementary Information

Supplementary Methods, Supplementary Tables 1–4, Supplementary Figures 1–6, Supplementary References

Supplementary Data 1

Cartesian coordinates and energies

Compound C′

Crystallographic data for compound C′

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Wang, H., Choi, I., Rogge, T. et al. Versatile and robust C–C activation by chelation-assisted manganese catalysis. Nat Catal 1, 993–1001 (2018). https://doi.org/10.1038/s41929-018-0187-1

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