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Nickel-catalysed anti-Markovnikov hydroarylation of unactivated alkenes with unactivated arenes facilitated by non-covalent interactions

Nature Chemistry volume 12, pages 276–283 (2020)Cite this article

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Abstract

Anti-Markovnikov additions to alkenes have been a longstanding goal of catalysis, and anti-Markovnikov addition of arenes to alkenes would produce alkylarenes that are distinct from those formed by acid-catalysed processes. Existing hydroarylations are either directed or occur with low reactivity and low regioselectivity for the n-alkylarene. Herein, we report the first undirected hydroarylation of unactivated alkenes with unactivated arenes that occurs with high regioselectivity for the anti-Markovnikov product. The reaction occurs with a nickel catalyst ligated by a highly sterically hindered N-heterocyclic carbene. Catalytically relevant arene- and alkene-bound nickel complexes have been characterized, and the rate-limiting step was shown to be reductive elimination to form the C–C bond. Density functional theory calculations, combined with second-generation absolutely localized molecular orbital energy decomposition analysis, suggest that the difference in activity between catalysts containing large and small carbenes results more from stabilizing intramolecular non-covalent interactions in the secondary coordination sphere than from steric hindrance.

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Fig. 1: Transition metal-catalysed hydroarylation of unactivated alkenes with unactivated arenes.
Fig. 2: Reaction development and characterization of [L4–Ni(η6-C6H6)].
Fig. 3: Observation and isolation of catalyst resting states.
Fig. 4: Mechanistic experiments.
Fig. 5: Computational investigations.

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Data availability

Crystallographic data for the structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers 1901576 ([L4–Ni(η6-C6H6)]), 1901577 (26) and 1901578 (25). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. All other data supporting the findings of this study are available within the Article and its Supplementary Information, or from the corresponding author upon reasonable request.

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Acknowledgements

We thank S. Arlow, C. Karmel and J. Wang for helpful discussions. We thank Y. Schramm for preliminary experiments. We acknowledge N. Settineri for X-ray crystallographic analysis. We thank M. Head-Gordon and M. Loipersberger for discussions on EDA calculations. This work was supported by the Director, Office of Science, of the U.S. Department of Energy under contract no. DE-AC02- 05CH11231, by the National Science Foundation (graduate research fellowship to N.I.S.) and by the Japan Society for the Promotion of Science (JSPS KAKENHI Grant Number JP15H05799). X-ray diffraction data were collected using an instrument funded by the NIH (S10-RR027172). Computations were performed on a computation cluster funded by the NIH (S10-OD023532). NMR spectroscopy was performed in the College of Chemistry’s NMR facility funded in part by the NIH (S10-OD024998).

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Authors and Affiliations

  1. Department of Chemistry, University of California, Berkeley, Berkeley, CA, USA

    Noam I. Saper, David W. Small & John F. Hartwig

  2. Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto, Japan

    Akito Ohgi, Kazuhiko Semba & Yoshiaki Nakao

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  1. Noam I. Saper
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Contributions

All authors conceived and designed the experiments. N.I.S., A.O. and K.S. performed the experiments. N.I.S. and D.W.S. performed the computations. All authors participated in discussion and N.I.S. J.F.H. and Y.N. co-wrote the manuscript.

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Correspondence to Yoshiaki Nakao or John F. Hartwig.

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Supplementary information

Supplementary Information

Experimental details, procedures and characterization data for all compounds and mechanistic experiments reported in this manuscript. Details on computational analysis and xyz coordinates of all structures.

Crystallographic data

Crystallographic data for compound 25. CCDC reference 1901578.

Crystallographic data

Crystallographic data for compound 26. CCDC reference 1901577.

Crystallographic data

Crystallographic data for compound [L4–Ni(η6-C6H6)]. CCDC reference 1901576.

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Saper, N.I., Ohgi, A., Small, D.W. et al. Nickel-catalysed anti-Markovnikov hydroarylation of unactivated alkenes with unactivated arenes facilitated by non-covalent interactions. Nat. Chem. 12, 276–283 (2020). https://doi.org/10.1038/s41557-019-0409-4

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