Transition metal-catalyzed cross-couplings are an important class of reactions that can be used for the construction of C-C bonds. In particular, the oxidative addition, ligand exchange, reductive elimination (OLR) catalytic sequence has established its privileged prominence as an especially versatile reaction manifold. Indeed, many pharmaceutically active agents have critically relied on this mode of reactivity as a key strategic imperative for synthetic planning and execution. However, despite its track record of synthetic utility, an acute issue that has plagued the OLR reaction manifold is the frequently required use of stoichiometric quantity of organometallic reagents. This can raise serious concerns over experimental reproducibility, operational safety, and waste management. The stoichiometric organometallic issue stems from the subjective and fixed choice of a halide (or pseudohalide) as the to-be-displaced ligand and a carbon-centered species as the displacing ligand (Scheme 1a). A strategic solution framework of molecular cross-coupling chemistry, with neutral molecules serving as the coupling partners, can be envisioned with the following guiding tenets: ligand exchange should occur (thermodynamically downhill) between heteroatom-centered species, with the displacing ligand subsequently capable of rearranging from the heteroatom-ligated to carbon-ligated mode (Scheme 1b). We speculate that a combination of acid-base and β-carbon elimination reactions would allow the implementation of these key steps. Our synthetic endeavor has validated this conjecture and herein, we wish to report a palladium-catalyzed coupling of amides and cyclopropanols for the synthesis of γ-diketones. The reaction can be rationalized by the following mechanistic sequence: the oxidative addition of amide to Pd(0) generates acyl and amido ligands; proton transfer exchanges amido ligand to cyclopropanolate; β-carbon elimination converts O-ligation to ring-opened, β-keto C-ligation; reductive elimination completes coupling between acyl and β-keto alkyl ligand fragments. This molecular cross-coupling reactivity represents a deviation from the routine synthetic modality adopted in amide activation chemistry. Significantly, the two carbonyl groups can be reduced highly efficiently, essentially translating the γ-diketone synthesis into an alkyl-alkyl coupling protocol.