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Catalytic C(sp2) homologation of alkylboranes

Nature Chemistry volume 17, pages 1418–1424 (2025)Cite this article

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Abstract

Organoboron compounds are important intermediates in organic synthesis, commonly used in metal-catalysed cross-coupling reactions. Their unique reactivity also allows modifications of their carbon framework with preservation of the valuable boryl group. Traditionally, these homologation reactions have been confined to the formation of alkyl boron compounds via C(sp3) insertion into a C–B bond. However, recent advancements in C(sp2)-insertive homologation highlight the potential of these reactions in synthesizing complex alkenes, despite current limitations in scope and control of the alkene geometry. Here we demonstrate a catalytic C(sp2)-insertive homologation for the regio- and diastereoselective synthesis of complex trisubstituted diborylalkenes from simple alkylboranes and alkynyl boronic esters. Our work demonstrates a broad reaction scope and application of the resulting products in modular and stereoselective synthesis of highly substituted alkenes. Furthermore, we provide evidence supporting a unique mechanism responsible for the excellent stereoselectivity observed in the reaction.

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Fig. 1: Homologation reactions of alkylboranes.
Fig. 2: Transformations of diborylalkene products.
Fig. 3: Mechanistic studies.

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Data availability

Crystallographic data for compound 29 are available free of charge from the Cambridge Crystallographic Data Centre under reference CCDC 2370487. All other data are available in the article or its Supplementary Information.

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Acknowledgements

Support has been provided by the National Institutes of Health (National Institute of General Medical Sciences grant no. R35GM158014 to G.L. and grant no. S10OD030224-01 to the University of Washington, Department of Chemistry NMR facility). We thank H. W. Kaminsky and S. M. Krajewski for determination of the X-ray crystal structure.

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  1. Department of Chemistry, University of Washington, Seattle, WA, USA

    Bradley W. Gardner & Gojko Lalic

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  1. Bradley W. Gardner
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B.W.G. conceived of, designed and performed the experiments. B.W.G. and G.L. co-wrote the paper.

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Correspondence to Gojko Lalic.

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Supplementary Information

Supplementary Tables 1–8, experimental procedures, product characterization data and NMR spectra.

Supplementary Data 1

Crystallographic data for compound 29; CCDC reference 2370487.

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Gardner, B.W., Lalic, G. Catalytic C(sp2) homologation of alkylboranes. Nat. Chem. 17, 1418–1424 (2025). https://doi.org/10.1038/s41557-025-01854-4

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