Benzylic C–H Radical Sulfation by Persulfates

Abstract

Sulfation is a highly valuable pathological and physiological process, yet it is often underappreciated considering the rather difficult accessibility of organosulfates. O-sulfonation (O–SO3), a conventional and still common way to make organosulfates, restricts its applicability to hydroxyl compounds and therein lies a major challenge of library construction. Here, we describe a benzylic C–H radical sulfation with persulfates via C–O bond formation. This strategy leverages modular control over the reactivity of persulfates and the stability of sulfate radicals by coutercations. K+/NH4+ stabilized sulfate radicals act as the oxidant to generate carbon-centered radicals from substrates, and activation of persulfates by NBu4+ provides O–O resource pool to facilitate C–OSO3- bond formation via a bimolecular homolytic substitution (SH2) process.