<i>Ex Situ</i> Generation of Sulfuryl Fluoride for the Synthesis of Aryl Fluorosulfates

A convenient transformation of phenols into the corresponding aryl fluorosulfates is presented: the first protocol to completely circumvent direct handling of gaseous sulfuryl fluoride (SO<sub>2</sub>F<sub>2</sub>). The proposed method employs 1,1′-sulfonyldiimidazole as a precursor to generate near-stoichiometric amounts of SO<sub>2</sub>F<sub>2</sub> gas using a two-chamber reactor. With NMR studies, it was shown that this <i>ex situ</i> gas evolution is extremely rapid, and a variety of phenols and hydroxylated heteroarenes were fluorosulfated in good to excellent yields.