Nickel-Catalyzed Electrophilic Amination of the Biphenylene C-C -Bond

A nickel-catalyzed three-component carboamination of the biphenylene C-C sigma-bond has been developed. Arylboronates and hydroxylamine derivatives work as carbon nucleophiles and nitrogen electrophiles, respectively, and the corresponding difunctionalized ring-opening products are obtained in good yields. The arylboronate nucleophile can be replaced with B(2)pin(2) (boron nucleophile) and H-Si(OMe)(3) (hydride nucleophile), thus allowing for the aminoboration and hydroamination of the biphenylene C-C sigma-bond under similar nickel catalysis.