Site‐Selective, Modular Diversification of Polyhalogenated Aryl Fluorosulfates (ArOSO(2)F) Enabled by an Air‐Stable Pd(I) Dimer

Since 2014, the interest in aryl fluorosulfates (ArOSO(2)F) as well as their implementation in powerful applications has continuously grown. In this context, the enabling capability of ArOSO(2)F will strongly depend on the substitution pattern of the arene, which ultimately dictates its overall function as drug candidate, material, or bio‐linker. This report showcases the modular, substrate‐independent, and fully predictable, selective functionalization of polysubstituted arenes bearing C−OSO(2)F, C−Br, and C−Cl sites, which makes it possible to diversify the arene in the presence of OSO(2)F or utilize OSO(2)F as a triflate surrogate. Sequential and triply selective arylations and alkylations were realized within minutes at room temperature, using a single and air‐stable Pd(I) dimer.