S N 2′-Type Difluoro- and Perfluoroalkylation of gem -Dichlorocyclobutenones Mediated by (DMPU) 2 Zn(Rf) 2

We report an S_N2'-type strategy for direct difluoromethylation and perfluoroalkylation of gem-dichlorocyclobutenones using (DMPU)₂Zn(Rf)₂ reagents. Difluoromethylation proceeds under metal-free conditions, whereas copper catalyst promotes perfluoroalkylation via transmetalation. The method tolerates diverse aryl, heteroaryl, and complex bioactive substrates, yielding chloro-fluoroalkylated cyclobutenones as versatile intermediates for further functionalization. This approach enables rapid access to polyfunctionalized fluorinated four-membered carbocycles, thus enriching the toolkit for the synthesis of fluorinated scaffolds relevant to medicinal chemistry and materials science.