General Base-Free Suzuki-Miyaura Cross-Coupling Reaction via Electrophilic Substitution Transmetalation

Meng Zhang^#¹, Jing-Ran Shan^#², Yuke Xie¹, Lanen Wei³, Haigen Xiong^{1

4}, Ge-Ning Xie¹, Ting Qi³, Qinqin Shi¹, K N Houk², Hui Huang^{1

4}

Affiliations

¹ College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing, 100049, P.R. China.
² Department of Chemistry and Biochemistry, University of California, Los Angeles, California, 90095, USA.
³ School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing, 100049, P.R. China.
⁴ School of Chemical Engineering and Technology, State Key Laboratory of Chemical Engineering and Low-Carbon Technology, Tianjin University, Tianjin, 300072, P.R. China.

^# Contributed equally.

PMID: 40692496
DOI: 10.1002/anie.202512496

General Base-Free Suzuki-Miyaura Cross-Coupling Reaction via Electrophilic Substitution Transmetalation

Meng Zhang et al. Angew Chem Int Ed Engl. 2025.

. 2025 Jul 22:e202512496.

doi: 10.1002/anie.202512496. Online ahead of print.

Authors

Meng Zhang^#¹, Jing-Ran Shan^#², Yuke Xie¹, Lanen Wei³, Haigen Xiong^{1

4}, Ge-Ning Xie¹, Ting Qi³, Qinqin Shi¹, K N Houk², Hui Huang^{1

4}

Affiliations

¹ College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing, 100049, P.R. China.
² Department of Chemistry and Biochemistry, University of California, Los Angeles, California, 90095, USA.
³ School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing, 100049, P.R. China.
⁴ School of Chemical Engineering and Technology, State Key Laboratory of Chemical Engineering and Low-Carbon Technology, Tianjin University, Tianjin, 300072, P.R. China.

^# Contributed equally.

PMID: 40692496
DOI: 10.1002/anie.202512496

Abstract

The transition-metal-catalyzed Suzuki-Miyaura cross-coupling (SMC) reaction of organoboron nucleophiles with aryl (pseudo)halide electrophiles is a reliable method for carbon-carbon bond formation. This reaction generally requires the use of an exogenous base to promote transmetalation process, which limits the substrate scope of the reaction due to undesired protodeboronation and functional group incompatibilities. Here, we established a base-free SMC reaction via a conceptually different electrophilic substitution transmetalation (EST). This transformation is applicable to a wide range of base-sensitive and sterically hindered organoborons. Key to this advance is the formation of a stable cationic palladium(II) or nickel(II) intermediate via experimental and theoretical investigations. In a broader context, this research further expands the synthetic boundary of cross-coupling chemistry.

Keywords: Base‐free; Electrophilic substitution transmetalation; Stable cationic intermediates; Suzuki‐Miyaura cross‐coupling.

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References

1. A. Suzuki, Angew. Chem. Int. Ed. 2011, 50, 6722–6737.
1. N. Miyaura, A. Suzuki, Chem. Rev. 1995, 95, 2457–2483.
1. D. G. Brown, J. Bostrom, J. Med. Chem. 2016, 59, 4443–4458.
1. C. Amatore, A. Jutand, G. Le Duc, Angew. Chem. Int. Ed. 2012, 51, 1379–1382.
1. A. J. Lennox, G. C. Lloyd‐Jones, Angew. Chem. Int. Ed. 2013, 52, 7362–7370.

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General Base-Free Suzuki-Miyaura Cross-Coupling Reaction via Electrophilic Substitution Transmetalation

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General Base-Free Suzuki-Miyaura Cross-Coupling Reaction via Electrophilic Substitution Transmetalation

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