In summary, a palladium-catalyzed molecular cross-coupling reaction between amides and cyclopropanols has been developed for the construction of γ-diketones. The synthesis is featured with a complete elimination of the stoichiometric organometallic reagent and base additive, thus ensuring a broad substrate compatibility. The reactivity of an amide can be programmed through the adjustment of electronic and steric environment around the N-atom, facilitating the establishment of a reactivity order chemistry set and potentiating the achievement of one-pot chemistry. This transformation can be further elaborated into an alkyl-alkyl coupling surrogate, providing an attractive alternative synthetic strategy for this to-a-certain-extent challenging reaction.