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Disclosed herein is the first general chemo‐ and site‐selective alkylation of C−Br bonds in the presence of COTf, C−Cl and other potentially reactive functional groups, using the air‐, moisture‐, and thermally stable dinuclear Pd I  catalyst, [Pd(μ‐I)PtBu 3 ] 2 . The bromo‐selectivity is independent of the substrate and the relative positioning of the competing reaction sites, and as such fully predictable. Primary and secondary alkyl chains were introduced with extremely high speed (<5 min reaction time) at room temperature and under open‐flask reaction conditions.

Palladium(I) Dimer Enabled Extremely Rapid and Chemoselective Alkylation of Aryl Bromides over Triflates and Chlorides in Air