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. 2025 Sep 8;64(37):e202512496.
doi: 10.1002/anie.202512496. Epub 2025 Jul 22.

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

Meng Zhang #  1 , Jing-Ran Shan #  2 , Yuke Xie  1 , Lanen Wei  3 , Haigen Xiong  1   4 , Ge-Ning Xie  1 , Ting Qi  3 , Qinqin Shi  1 , K N Houk  2 , Hui Huang  1   4
Affiliations

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

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

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

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