Electrochemical Generation of Hypervalent Bromine(III) Compounds

In sharp contrast to hypervalent iodine(III) compounds, the isoelectronic bromine(III) counterparts have been little studied to date. This knowledge gap is mainly attributed to the difficult‐to‐control reactivity of λ 3 ‐bromanes as well as to their challenging preparation from the highly toxic and corrosive BrF 3 precursor. In this context, we present a straightforward and scalable approach to chelation‐stabilized λ 3 ‐bromanes by anodic oxidation of parent aryl bromides possessing two coordinating hexafluoro‐2‐hydroxypropanyl substituents. A series of para ‐substituted λ 3 ‐bromanes with remarkably high redox potentials spanning a range from 1.86 V to 2.60 V vs. Ag/AgNO 3 was synthesized by the electrochemical method. We demonstrate that the intrinsic reactivity of the bench‐stable bromine(III) species can be unlocked by addition of a Lewis or a Brønsted acid. The synthetic utility of the λ 3 ‐bromane activation is exemplified by oxidative C−C, C−N, and C−O bond forming reactions.