Reagent-controlled regiodivergent ring-opening reactions of trichloromethylcyclopropane carboxylates have been developed. The regioselectivity of bond cleavage is completely controlled by the proper choice of silver salts; the treatment of trichloromethylcyclopropane with AgBF4 led to C2-C3 bond cleavage and fluorination to afford fluorinated β,γ-unsaturated ester with high stereoselectivity, while the reaction with AgOAc in THF gave a γ,δ-unsaturated ester through the reductive cleavage of the C1-C2 bond.
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