Nickel catalyzed regio- and stereoselective arylation and methylation of allenamides via coupling reactions. An experimental and computational study

Abstract

The nickel catalyzed regio- and stereoselective condensation of boronic acids to allenamides is documented as a novel synthetic route to stereochemically defined tri-substituted enamides. The protocol has been implemented into a three-component variant intercepting the in situ formed allyl-Ni intermediate with a range of aldehydes. Additionally, evidence for the effective extension of this methodology to Me₂Zn is documented. Full rationale on the mechanism as well as its stereochemical outcome is provided by a synergistic experimental/computational approach.