Nucleophilic Deoxyfluorination of Phenols via Aryl Fluorosulfonate Intermediates.

This report describes a method for the deoxyfluorination of phenols with sulfuryl fluoride (SOF) and tetramethylammonium fluoride (NMeF) via aryl fluorosulfonate (ArOFs) intermediates. We first demonstrate that the reaction of ArOFs with NMeF proceeds under mild conditions (often at room temperature) to afford a broad range of electronically diverse and functional group-rich aryl fluoride products. This transformation was then translated to a one-pot conversion of phenols to aryl fluorides using the combination of SOF and NMeF. Ab initio calculations suggest that carbon-fluorine bond formation proceeds via a concerted transition state rather than a discrete Meisenheimer intermediate.