New Chemical Transformations Involving SO₂F₂‐Mediated Alcohol Activation

Abstract Sulfuryl fluoride is a gas produced on a multi‐ton scale for its use as a fumigant. In the last decades, it has gained interest in organic synthesis as a reagent with unique properties in terms of stability and reactivity when compared to other sulfur‐based reagents. Sulfuryl fluoride has not only been used for sulfur‐fluoride exchange (SuFEx) chemistry but also encountered applications in classic organic synthesis as an efficient activator of both alcohols and phenols, forming a triflate surrogate, namely a fluorosulfonate. A long‐standing industrial collaboration in our research group drove our work on the sulfuryl fluoride‐mediated transformations that will be highlighted below. We will first describe recent works on metal‐catalyzed transformations from aryl fluorosulfonates while emphasizing the one‐pot processes from phenol derivatives. In a second section, nucleophilic substitution reactions on polyfluoroalkyl alcohols will be discussed and the value of polyfluoroalkyl fluorosulfonates in comparison to alternative triflate and halide reagents will be brought to light.