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Electrochemical Generation of Hypervalent Bromine(III) Compounds
Author(s) -
Sokolovs Igors,
Mohebbati Nayereh,
Francke Robert,
Suna Edgars
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202104677
Subject(s) - hypervalent molecule , bromine , chemistry , reactivity (psychology) , electrochemistry , context (archaeology) , redox , aryl , oxidation state , iodine , combinatorial chemistry , inorganic chemistry , organic chemistry , catalysis , alkyl , electrode , medicine , paleontology , alternative medicine , pathology , biology
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.