Electrochemistry and Reactivity of Chelation‐stabilized Hypervalent Bromine(III) Compounds

Hypervalent bromine(III) reagents possess a higher electrophilicity and a stronger oxidizing power compared to their iodine(III) counterparts. Despite the superior reactivity, bromine(III) reagents have a reputation of hard‐to‐control and difficult‐to‐synthesize compounds. This is partly due to their low stability, and partly because their synthesis typically relies on the use of the toxic and highly reactive BrF3 as a precursor. Recently, we proposed chelation‐stabilized hypervalent bromine(III) compounds as a possible solution to both problems. First, they can be conveniently prepared by electro‐oxidation of the corresponding bromoarenes. Second, the chelation endows bromine(III) species with increased stability while retaining sufficient reactivity, comparable to that of iodine(III) counterparts. Finally, their intrinsic reactivity can be unlocked in the presence of acids. Herein, an in‐depth mechanistic study of both the electrochemical generation and the reactivity of the bromine(III) compounds is disclosed, with implications for known applications and future developments in the field.Deutsche Forschungsgemeinschaft http://dx.doi.org/10.13039/501100001659European Regional Development Fund http://dx.doi.org/10.13039/501100008530HORIZON EUROPE European Research Council http://dx.doi.org/10.13039/100019180Estonian Research Competency Council http://dx.doi.org/10.13039/501100005189Peer Reviewe