Site-Selective, Modular Diversification of Polyhalogenated Aryl Fluorosulfates (ArOSO₂ F) Enabled by an Air-Stable Pd^I Dimer

Since 2014, the interest in aryl fluorosulfates (ArOSO₂ F) as well as their implementation in powerful applications has continuously grown. In this context, the enabling capability of ArOSO₂ 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-OSO₂ F, C-Br, and C-Cl sites, which makes it possible to diversify the arene in the presence of OSO₂ F or utilize OSO₂ 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.