摘要：MengZhang1+, Jing-Ran Shan2+,YukeXie1LanenWei3,HaigenXiong1,4, Ge-Ning Xie1, Ting Qi3,QinqinShi,* K. N. Houk,2*and Hui Huang1,4*

转自：康龙化成

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

Meng Zhang1+, Jing-Ran Shan2+, Yuke Xie1LanenWei3, Haigen Xiong1,4, Ge-Ning Xie1, Ting Qi3, Qinqin Shi,* K. N. Houk,2* and Hui Huang1,4*

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

—Angew. Chem. Int. Ed. 2025, e202512496

Recommended by Bingbing Chang_MC5

KEY WORDS:Suzuki-Miyaura cross-coupling (SMC),Pdcatalysis,Nicatalysis(反应类型), C(sp2)–C(sp2), C(sp)-C(sp3) (成键类型),organoborons, thianthrenium (TT) salt, sulfonium salt, triflate (原料), biaryl (产物), base free, electrophilic substitution transmetalation(EST) (其他)

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 compatibilities. Here, Prof. Hui Huang et al. 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.

Background

Substrate scope (selected)

Prof. Hui Huang et al. have established a base-free SMC reaction of general (pseudo)halide reagents with organoborons, which rendered a wide substrate scope including steric hinderance and base sensitive substrates exemplified by over 100 compounds. The experimental and theoretical studies revealed a unique ESTprocess, enabled by a stable transition metal cation intermediate. Therefore, this study provides a general and environmentally friendly method to construct C─C bonds with excellent functional group compatibility.

来源：新浪财经