Ambiphilic cross-coupling with aryl-bismuth reagents | Nature

Subjects

- Homogeneous catalysis

- Synthetic chemistry methodology

Abstract

Cross-coupling reactions traditionally permit the formation of Ar-Ar bonds between an aryl nucleophile and an aryl electrophile under transition metal catalysis1,2. The high selectivity of the myriad of couplings known to date relies on a tailored combination of nucleophilic and electrophilic coupling partners, enabled by the mechanistic distinction between nucleophiles and electrophiles, which undergo fundamentally different catalytic steps.3 Here, we report ambiphilic aryl-bismuth reagents that can behave as either nucleophiles or electrophiles in transition metal-catalysed cross-couplings, fundamentally breaking from this dichotomy in reactivity. Their ambiphilic reactivity arises from their ability to engage in both oxidative addition and transmetalation processes with transition metal complexes, as demonstrated by stoichiometric and mechanistic studies. By demonstrating that a single aryl reagent can engage in both canonical elementary steps, this work challenges the long-standing assumption that intrinsic bond polarity rigidly dictates mechanistic role in cross-coupling chemistry.

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Author information

Authors and Affiliations

- Max-Planck-Institut für Kohlenforschung, Mülheim an der Ruhr, Germany

Byeongdo Roh, Benedict A. Williams & Josep Cornella

Authors- Byeongdo RohView author publications

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- Benedict A. WilliamsView author publications

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- Josep CornellaView author publications

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Corresponding author

Correspondence to

Josep Cornella.

Supplementary information

Supplementary Information (download PDF )

Supplementary Information containing the following sections: 1. General Experimental Details; 2. Procedures for the Preparation of Starting Materials; 3. Optimization of Reaction Conditions; 4. General Procedures for Ambiphilic Cross-Coupling; 5. Synthesis and Characterization of the Products; 6. Mechanistic Investigations; 7. Convergent Synthesis of Ambiphilic N,C,N-Pincer Aryl-Bismuth Compounds; 8. References; and 9. NMR spectra for Isolated Products and Substrates.

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Cite this article

Roh, B., Williams, B.A. & Cornella, J. Ambiphilic cross-coupling with aryl-bismuth reagents.

Nature (2026). https://doi.org/10.1038/s41586-026-10486-8

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- Received: 28 October 2025

- Accepted: 02 April 2026

- Published: 09 April 2026

- DOI: https://doi.org/10.1038/s41586-026-10486-8

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