Ligand‐Controlled Nickel‐Catalyzed Regiodivergent Cross‐Electrophile Alkyl‐Alkyl Couplings of Alkyl Halides

Abstract

AbstractFunctionalizing specific positions on a saturated alkyl molecule is a key challenge in synthetic chemistry. Herein, a ligand‐controlled regiodivergent alkylations of alkyl bromides at different positions by Ni‐catalyzed alkyl‐alkyl cross‐electrophile coupling with the second alkyl bromides has been developed. The reaction undergoes site‐selective isomerization on one alkyl bromides in a controlled manner, providing switchable access to diverse alkylated structures at different sites of alkyl bromides. The reaction occurs at three similar positions with excellent chemo‐ and regioselectivity, representing a remarkable ligand tuned reactivity between alkyl‐alkyl cross‐coupling and nickel migration along the hydrocarbon side chain. This reaction offers a catalytic platform to diverse saturated architectures by alkyl‐alkyl bond‐formation from identical starting materials.