Construction of congested Csp(3)–Csp(3) bonds by a formal Ni-catalyzed alkylboration

Through the combination of a Ni-catalyzed alkene alkenylboration followed by hydrogenation, the synthesis of congested Csp(3)–Csp(3)-bonds can be achieved. Conditions have been identified that allow for the use of both alkenyl-bromides and -triflates. In addition, the hydrogenation creates another opportunity for stereocontrol, thus allowing access to multiple stereoisomers of the product. Finally, the method is demonstrated in the streamlined synthesis of a biologically relevant molecule.