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

Abstract

Since 2014, the interest in aryl fluorosulfates (ArOSO ₂F) as well as their implementation in powerful applications has continuously grown. In this context, the enabling capability of ArOSO ₂F 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 ₂F, C−Br, and C−Cl sites, which makes it possible to diversify the arene in the presence of OSO ₂F or utilize OSO ₂F 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.

Abstract

Diversity: The rapid, modular, substrate‐independent and fully predictable functionalization of polysubstituted arenes bearing C−OSO ₂F, C−Br, and C−Cl sites at room temperature is showcased. In this way the arene unit can be functionalized in the presence of a fluorosulfate group or the latter can serve as a triflate surrogate.