Nickel-catalyzed difunctionalization of allyl moieties using organoboronic acids and halides with divergent regioselectivities.

ABSTRACT: 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-2-amine is achieved when aryl and methyl iodides are utilized. In contrast, the use of alkyl bromides with ?-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 1,2-alkenylcarbonation 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.

SUBMITTER: Li W 

PROVIDER: S-EPMC5869318 | biostudies-literature | 2018 Jan

REPOSITORIES: biostudies-literature