Nickel-catalyzed difunctionalization of allyl moieties using organoboronic acids and halides with divergent regioselectivities† †Electronic supplementary information (ESI) available. CCDC 1563066. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc03149a

Efficient difunctionalization of alkenes allows the rapid construction of molecular complexity from simple building blocks in organic synthesis. We present herein a nickel-catalyzed dicarbofunctionalization of alkenes using readily available organoboronic acids and organic halides in a three-component fashion. In particular, an unprecedented regioselectivity of the 1,3-dicarbofunctionalization of N-allylpyrimidin-2amine is achieved when aryl and methyl iodides are utilized. In contrast, the use of alkyl bromides with b-hydrogens results in 1,3-hydroarylation or oxidative 1,3-diarylation. Preliminary mechanistic studies suggest an isomerization involving nickel hydride in the 1,3-difunctionalization reactions. On the other hand, the use of alkenyl or alkynyl halides promotes alternative regioselectivities to deliver 1,2alkenylcarbonation or intriguing 2,1-alkynylcarbonation products. Such 2,1-alkynylarylation is also applicable to N-allylbenzamide as a different class of substrates. Overall, this nickel-catalyzed process proves to be powerful in delivering versatile difunctionalized compounds using readily available reagents/ catalysts and a simple procedure.