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A multicomponent synthesis of stereodefined olefins via nickel catalysis and single electron/triplet energy transfer

Nature Catalysis volume 2, pages 678–687 (2019)Cite this article

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Abstract

Unsaturated carbon–carbon bonds are one of the most common and important structural motifs in many organic molecules, stimulating the continuous development of general, efficient and practical strategies for their functionalization. Here, we report a one-pot difunctionalization of alkynes via a photoredox/nickel dual-catalysed three-component cross-coupling reaction under mild conditions, providing access to a series of highly important tri-substituted alkenes. Notably, in contrast to traditional methods that are based on the steric hindrance of the substrates to control the reaction selectivity, both E- and Z-isomers of tri-substituted alkenes, which are often energetically close, can be obtained by choosing an appropriate photocatalyst with a suitable triplet state energy. Beyond the immediate practicality of this transformation, this newly developed methodology might inspire the development of diverse and important one-pot functionalizations of carbon–carbon multiple bonds via photoredox and transition-metal dual-catalysed multicomponent reactions.

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Fig. 1: Multicomponent cross-coupling reaction under mild conditions and its main challenges.
Fig. 2: Mechanistic design of the newly developed three-component reaction.
Fig. 3: Substrate scope of aryl halides and alkynes for the photoredox/nickel dual-catalysed aryl-sulfonylation of alkynes using Ru photocatalyst 3.
Fig. 4: Substrate scope of sodium sulfinates and complex molecules for the photoredox/nickel dual catalysed aryl-sulfonylation of alkynes using Ru photocatalyst 3.
Fig. 5: Substrate scope for the photoredox/nickel dual-catalysed aryl-sulfonylation of alkynes using Ir photocatalyst 2.
Fig. 6: Gram-scale reactions and applications.
Fig. 7: Mechanistic investigations.
Fig. 8: Computational investigation of the nickel catalytic cycle.

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Data availability

The X-ray crystallographic coordinates for structures of 5 and 87 reported in this Article have been deposited at the Cambridge Crystallographic Data Centre (CCDC) under deposition numbers CCDC 1914140 (5) and 1914141 (87). These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. Experimental procedures and characterization of the new compounds are available in the Supplementary Information. All other data are available from the authors upon reasonable request.

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Acknowledgements

The authors thank D. Wöll and O. Nevskyi for assistance with measuring the emission spectra of the photocatalysts. H.Y. thanks the China Scholarship Council. C.Z., B.M., L.C. and M.R. acknowledge King Abdullah University of Science and Technology (KAUST) for support and the KAUST Supercomputing Laboratory for providing computational resources of the supercomputer Shaheen II. The research leading to these results has received funding from the European Research Council under the European Union’s Seventh Framework Programme (FP/2007-2013) and ERC grant agreement no. 617044 (SunCatChem).

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Author notes

  1. These authors contributed equally: Chen Zhu, Huifeng Yue.

Authors and Affiliations

  1. KAUST Catalysis Center, King Abdullah University of Science and Technology, Thuwal, Saudi Arabia

    Chen Zhu, Huifeng Yue, Bholanath Maity, Luigi Cavallo & Magnus Rueping

  2. Institute of Organic Chemistry, RWTH Aachen University, Aachen, Germany

    Chen Zhu, Huifeng Yue, Iuliana Atodiresei & Magnus Rueping

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Contributions

C.Z., H.Y. and M.R. conceived and designed the experiments. C.Z. and H.Y. performed and analysed the experiments. I.A. conducted X-ray crystal structure analysis. C.Z., B.M. and L.C. performed the theoretical calculations. All authors discussed the results and contributed to the manuscript.

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Correspondence to Luigi Cavallo or Magnus Rueping.

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Supplementary information

Supplementary Information

Supplementary methods, Supplementary Figs. 1–19, Supplementary Tables 1–7, Supplementary references

Supplementary Data 1

Cartesian coordinates and energies of calculated structures

Compound 5

Crystallographic data for compound 5

Compound 87

Crystallographic data for compound 87

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Zhu, C., Yue, H., Maity, B. et al. A multicomponent synthesis of stereodefined olefins via nickel catalysis and single electron/triplet energy transfer. Nat Catal 2, 678–687 (2019). https://doi.org/10.1038/s41929-019-0311-x

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