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Mar 13, 2025

Aryl halide cross-coupling via formate-mediated transfer hydrogenation | Nature Chemistry

Nature Chemistry (2025)Cite this article 2 Altmetric Metrics details Transfer hydrogenation is widely practised across all segments of chemical industry, yet its application to aryl halide reductive

Nature Chemistry (2025)Cite this article

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Transfer hydrogenation is widely practised across all segments of chemical industry, yet its application to aryl halide reductive cross-coupling is undeveloped because of competing hydrogenolysis. Here, exploiting the distinct reactivity of PdI species, an efficient catalytic system for the reductive cross-coupling of activated aryl bromides with aryl iodides via formate-mediated hydrogen transfer is described. These processes display orthogonality with respect to Suzuki and Buchwald–Hartwig couplings, as pinacol boronates and anilines are tolerated and, owing to the intervention of chelated intermediates, are effective for challenging 2-pyridyl systems. Experimental and computational studies corroborate a unique catalytic cycle for reductive cross-coupling where the PdI precatalyst, [Pd(I)(PtBu3)]2, is converted to the dianionic species, [Pd2I4][NBu4]2, from which aryl halide oxidative addition is more facile. Rapid, reversible Pd-to-Pd transmetallation delivers mixtures of iodide-bridged homo- and hetero-diarylpalladium dimers. The hetero-diarylpalladium dimers are more stable and have lower barriers to reductive elimination, promoting high levels of cross-selectivity.

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All data relating to materials and methods, experimental procedures, mechanistic studies, characterization data for all new compounds (1H NMR, 13C NMR, 19F NMR, 31P NMR, IR and HRMS), computational details and additional computational results are available in the Supplementary Information. Crystallographic data for [Pd2I6][NBu4]2 have been deposited at the Cambridge Crystallographic Data Centre (CCDC) under deposition number 2380764. Copies of data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/.

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The Robert A. Welch Foundation (F-0038) and the National Institutes of Health (NIH)-National Institute of General Medical Sciences (NIGMS) (RO1-GM069445 and R35 GM128779) are acknowledged for partial support of this research. Genentech is acknowledged for summer predoctoral internship support (Y.C.). N.S.T. is supported in part by the NIH-NIGMS (R35GM-133566). Instrumentation for the University of Minnesota (UMN) Chemistry NMR facility was supported from a grant through the NIH (S10OD011952) and the UMN Department of Chemistry Mass Spectrometry Laboratory is supported by the Office of the Vice President for Research, College of Science and Engineering and the Department of Chemistry at UMN, as well as the National Science Foundation (NSF) (CHE-1336940). X-ray diffraction experiments were performed by A. Lovstedt and G. Murphy with a diffractometer purchased through a grant from NSF/MRI (1229400) and the UMN. DFT calculations were carried out at the University of Pittsburgh Center for Research Computing and the Advanced Cyberinfrastructure Co-ordination Ecosystem: Services and Support (ACCESS) programme, supported by NSF award numbers OAC-2117681, OAC-1928147 and OAC-1928224. We thank M. Huestis, M. Ashley and C. Stivala for helpful scientific discussions.

These authors contributed equally: Yoon Cho, Yu-Hsiang Chang, Kevin P. Quirion, Zachary H. Strong.

Department of Chemistry, University of Texas at Austin, Austin, TX, USA

Yoon Cho, Yu-Hsiang Chang, Zachary H. Strong, Zachary J. Dubey, Seoyoung Lee & Michael J. Krische

Department of Chemistry, University of Pittsburgh, Pittsburgh, PA, USA

Kevin P. Quirion & Peng Liu

Department of Synthetic Molecule Process Chemistry, Genentech, South San Francisco, CA, USA

Nam Nguyen & Nicholas A. White

Department of Chemistry, University of Minnesota-Twin Cities, Minneapolis, MN, USA

Natalie S. Taylor & Jessica M. Hoover

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Y.C., Y.-H.C., Z.J.D. and S.L. designed the project under the guidance of N.A.W. and M.J.K. Y.C., Y.-H.C., Z.H.S., Z.J.D. and S.L. carried out experimental work and mechanistic studies notwithstanding Supplementary Information section XI. K.P.Q. performed calculations under the guidance of P.L. N.S.T. carried out mechanistic studies described in Supplementary Information section XI under the guidance of J.M.H. N.N. performed the HTE experiments. P.L. and M.J.K. composed the manuscript with input from all authors.

Correspondence to Jessica M. Hoover, Nicholas A. White, Peng Liu or Michael J. Krische.

The authors declare no competing interests.

Nature Chemistry thanks Corinne Gosmini, Kevin Shaughnessy and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–11, detailed experimental procedures, optimization, characterization and computational data.

Crystallographic data for compound [Pd2I6][NBu4]2; CCDC reference 2380764.

Cartesian coordinates raw file for all computations.

Checkcif file for [Pd2I6][NBu4]2.

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Cho, Y., Chang, YH., Quirion, K.P. et al. Aryl halide cross-coupling via formate-mediated transfer hydrogenation. Nat. Chem. (2025). https://doi.org/10.1038/s41557-024-01729-0

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Received: 25 June 2024

Accepted: 19 December 2024

Published: 11 March 2025

DOI: https://doi.org/10.1038/s41557-024-01729-0

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