Nickel(0)-catalyzed coupling of vinylzirconiums to α-bromo-α,α-difluoro esters. Convenient generation of a functionalized allyldifluoro moiety

Abstract

Vinylzirconium reagents couple with α-bromo-α,α-difluoro esters in the presence of a Ni(PPh 3) 4 catalyst to form alkenyl difluoro esters in good yields. This reaction exemplifies a novel mode of reactivity for α-bromo-α,α-difluoro esters wherein the inherent electrophilicity of the carbon–bromine bond is utilized in the course of the reaction rather than being formally reduced in Reformatzsky-type reactions. The choice of ester group in the reactant is critical to the success of this reaction with the isopropyl group, formed via a novel transesterification procedure, giving the best yields.