The preparation of HCF 2CdX and HCF 2ZnX via direct insertion into the carbon halogen bond of CF 2HY (Y = Br, I)

Abstract

The difluoromethylcadmium and zinc reagents have been prepared in DMF via direct insertion of Cd 0 into the carbon halogen bond of CF 2HY (Y = Br, I). These reagents are stable at 65–75 °C and exhibit prolonged stability and activity at room temperature. Metathesis of the difluoromethylcadmium reagents with Cu(I)X (X = Br, Cl) at −55 °C rapidly produces difluoromethylcopper. The copper reagent is significantly less stable than the cadmium or zinc reagent and rapidly decomposes at room temperature. The difluoromethylcadmium and copper reagents exhibit good reactivity with allylic halides, propargylic derivatives and 1-iodoalkynes to provide good yields of the corresponding difluoromethylalkenes, difluoromethylallenes and difluoromethyl-2-alkynes. Alkylation is successful only with reactive alkyl halides. Generally, the difluoromethylcopper reagent is more reactive than the difluoromethylcadmium reagent and generally exhibits higher regioselectivity in reactions that can occur by either α- or γ-attack.