Ni-catalyzed ring-opening hydrocyanation of methylenecyclopropanes toward cyano-substituted quaternary carbon centers

Transition-metal-catalyzed hydrofunctionalization of methylenecyclopropanes represents a useful transformation, typically yielding 1,2-hydrofunctionalization products as the major outcome. In this work, we report an unprecedented, highly selective nickel-catalyzed hydrocyanation of methylenecyclopropanes that affords 1,4-hydrofunctionalization products, forming acyclic cyano-substituted quaternary carbon centers. Mechanistic studies suggest that this reaction proceeds via a β-carbon elimination process involving a diene intermediate. DFT calculations further revealed that the regioselectivity for quaternary carbon center formation was controlled by a delicate interplay of steric and noncovalent interactions during the C–CN reductive elimination step.