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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 thei...

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Autores principales: Mohebbati, Nayereh, Sokolovs, Igors, Woite, Philipp, Lõkov, Märt, Parman, Elisabeth, Ugandi, Mihkel, Leito, Ivo, Roemelt, Michael, Suna, Edgars, Francke, Robert
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9401590/
https://www.ncbi.nlm.nih.gov/pubmed/35510557
http://dx.doi.org/10.1002/chem.202200974
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author Mohebbati, Nayereh
Sokolovs, Igors
Woite, Philipp
Lõkov, Märt
Parman, Elisabeth
Ugandi, Mihkel
Leito, Ivo
Roemelt, Michael
Suna, Edgars
Francke, Robert
author_facet Mohebbati, Nayereh
Sokolovs, Igors
Woite, Philipp
Lõkov, Märt
Parman, Elisabeth
Ugandi, Mihkel
Leito, Ivo
Roemelt, Michael
Suna, Edgars
Francke, Robert
author_sort Mohebbati, Nayereh
collection PubMed
description 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 BrF(3) 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.
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spelling pubmed-94015902022-08-26 Electrochemistry and Reactivity of Chelation‐stabilized Hypervalent Bromine(III) Compounds Mohebbati, Nayereh Sokolovs, Igors Woite, Philipp Lõkov, Märt Parman, Elisabeth Ugandi, Mihkel Leito, Ivo Roemelt, Michael Suna, Edgars Francke, Robert Chemistry Research Articles 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 BrF(3) 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. John Wiley and Sons Inc. 2022-06-10 2022-07-26 /pmc/articles/PMC9401590/ /pubmed/35510557 http://dx.doi.org/10.1002/chem.202200974 Text en © 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH https://creativecommons.org/licenses/by-nc-nd/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc-nd/4.0/ (https://creativecommons.org/licenses/by-nc-nd/4.0/) License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made.
spellingShingle Research Articles
Mohebbati, Nayereh
Sokolovs, Igors
Woite, Philipp
Lõkov, Märt
Parman, Elisabeth
Ugandi, Mihkel
Leito, Ivo
Roemelt, Michael
Suna, Edgars
Francke, Robert
Electrochemistry and Reactivity of Chelation‐stabilized Hypervalent Bromine(III) Compounds
title Electrochemistry and Reactivity of Chelation‐stabilized Hypervalent Bromine(III) Compounds
title_full Electrochemistry and Reactivity of Chelation‐stabilized Hypervalent Bromine(III) Compounds
title_fullStr Electrochemistry and Reactivity of Chelation‐stabilized Hypervalent Bromine(III) Compounds
title_full_unstemmed Electrochemistry and Reactivity of Chelation‐stabilized Hypervalent Bromine(III) Compounds
title_short Electrochemistry and Reactivity of Chelation‐stabilized Hypervalent Bromine(III) Compounds
title_sort electrochemistry and reactivity of chelation‐stabilized hypervalent bromine(iii) compounds
topic Research Articles
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9401590/
https://www.ncbi.nlm.nih.gov/pubmed/35510557
http://dx.doi.org/10.1002/chem.202200974
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