Nickel-Catalyzed Enantioselective Three-Component 1,2-Alkylarylation of Alkenes with Arylboronic Acids as Arylation Reagents

In recent years, Ni-catalyzed enantioselective radical relay three-component 1,2-alkylarylation of easily accessible alkenes has attracted significant attention. However, only aryl halides or aryl zinc reagents have been employed as arylation reagents in previous reports. With our continuous interest in organo-boron chemistry, herein, we report a redox-neutral protocol of this type of reaction, with easy-to-handle, air- and moisture-stable, and commercially available arylboronic acids as arylation reagents. The high stability of arylboronic acids also caused big problems, for example, slow transmetalation and low reactivity. To overcome these problems, we chose to use more electron-rich biimidazoline (BiIm) ligands, and we were able to develop a 4-Cl-Ph-substituted BiIm ligand, which gives good efficiency and enantioselectivity. Through our approach, 23 different arylboronic and heteroarylboronic acids have been demonstrated as efficient coupling partners, and a couple of easily accessible alkenes have been dicarbofunctionalized in good yields and enantiomeric excesses under mild conditions.