Abstract
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.