Abstract Palladium-and nickel-catalyzed cross-coupling recations of unactivated alkyl bromides with diboron reagents have been developed as practical methods for the synthesis of primary and secondary alkylboronic esters. These reactions extend the concept and utility of Pd-and Ni-catalyzed cross-coupling of aliphatic electrophiles. They also show different substrate selectivity and ligand dependence as compared to the recently reported Cu- ...