Abstract: | Potassium acyltrifluoroborates (KATs) are increasingly important functional groups, and general methods for their preparation are of great current interest. We report a bifunctional iminium reagent bearing both a tin nucleophile and a trifluoroborate, which was applied in chemoselective Pd0‐catalyzed Migita–Kosugi–Stille cross‐coupling reactions owith aryl and vinyl halides. This method gives access to previously inaccessible aromatic and α,β‐unsaturated acyltrifluoroborates, including precursors to amino‐acid derived KATs. |