General Base‐Free Suzuki‐Miyaura Cross‐Coupling Reaction via Electrophilic Substitution Transmetalation
Abstract
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.
Article Details
Authors (10)
Meng Zhang
Jing‐Ran Shan
Department of Chemistry and Biochemistry University of California Los Angeles California 90095 USA
Yuke Xie
College of Materials Science and Opto‐Electronic Technology University of Chinese Academy of Sciences Beijing 100049 P.R. China
Lanen Wei
School of Chemical Sciences University of Chinese Academy of Sciences Beijing 100049 P.R. China
Haigen Xiong
College of Materials Science and Opto‐Electronic Technology University of Chinese Academy of Sciences Beijing 100049 P.R. China
Ge‐Ning Xie
College of Materials Science and Opto‐Electronic Technology University of Chinese Academy of Sciences Beijing 100049 P.R. China
Ting Qi
Qinqin Shi
College of Materials Science and Opto-Electronic Technology, University of Chinese Academy of Sciences
K. N. Houk
Hui Huang
Center of Basic Molecular Science (CBMS), Department of Chemistry