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Nickel-catalysed hydrodimerization of unactivated terminal alkenes

Nature Synthesis volume 2, pages 364–372 (2023)Cite this article

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Abstract

Site-selective homo- and cross-hydrodimerization of terminal alkenes has remained a long-standing challenge in organic synthesis. Metal-hydride-catalysed selective dimerization, oligomerization or polymerization methods are often limited to electronically biased or small alkene substrates. Here we report the development of a nickel-catalysed protocol that enables selective homo- and cross-dimerization of unactivated linear and sterically congested terminal alkenes to afford linear alkyl‒alkyl products in good yields and high linear/branched selectivity. The process is tolerant of a range of functionalities including heteroatoms, saturated heterocycles and bioactive motifs. Mechanistic experiments reveal that the co-oxidants we used, CuBr2 and di-tert-butyl peroxide, probably convert dialkyl‒Ni(II) intermediates to the corresponding Ni(III) species through a single-electron-transfer process. This oxidative step avoids decomposition of thermally labile dialkyl‒Ni(II) intermediates and promotes the formation of hydrodimerization products by reductive elimination of the Ni(III) complex. Without CuBr2, high branched selectivity was achieved, affording the methyl-branched products—which are typically difficult to synthesize—in good yields.

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Fig. 1: MH-catalysed alkene dimerization and nickel-catalysed linear hydrodimerization.
Fig. 2: Linear and methyl-branched hydrodimerization of terminal alkenes.
Fig. 3: The mechanistic studies and proposals for the hydrodimerization of terminal alkenes.

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

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Acknowledgements

The authors acknowledge the financial support of the National Natural Science Foundation of China (21871173). We thank J.L. Sessler (University of Texas), D. Vicic (Lehigh University) and X. Lu (USTC, China) for helpful discussions.

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Authors and Affiliations

  1. Center for Supramolecular Chemistry and Catalysis, Department of Chemistry and School of Materials Science and Engineering, Shanghai University, Shanghai, China

    Li Cheng, Jiandong Liu, Yunrong Chen & Hegui Gong

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  1. Li Cheng
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Contributions

H.G. designed the project and drafted the manuscript. L.C. and J.L. performed the experiments and contributed equally. Y.C. conducted mass spectroscopic studies. All the authors participated in the preparation of the manuscript.

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Correspondence to Hegui Gong.

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Supplementary methods, Figs. 1–21, Tables 1–6, discussion and references.

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Cheng, L., Liu, J., Chen, Y. et al. Nickel-catalysed hydrodimerization of unactivated terminal alkenes. Nat. Synth 2, 364–372 (2023). https://doi.org/10.1038/s44160-023-00239-0

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