Directed nickel-catalyzed regio- and diastereoselective arylamination of unactivated alkenes

Few methods have been reported for intermolecular arylamination of alkenes, which could provide direct access to important arylethylamine scaffolds. Herein, we report an intermolecular syn -1,2-arylamination of unactivated alkenes with arylboronic acids and O -benzoylhydroxylamine electrophiles with Ni(II) catalyst. The cleavable bidentate picolinamide directing group facilitates formation of stabilized 4-, 5- or 6-membered nickelacycles and enables the difunctionalization of diverse alkenyl amines with high levels of regio-, chemo- and diastereocontrol. This general and practical protocol is compatible with broad substrate scope and high functional group tolerance. The utility of this method is further demonstrated by the site-selective modification of pharmaceutical agents. Few methods exist to add a carbon and nitrogen atom across an unfunctionalized alkene. Here the authors show a method to regio- and diastereoselectively add aryl and amino groups to terminal and internal alkenes, via nickel catalysis and a removable directing group.