Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2021 Jul 12;60(29):15832-15837.
doi: 10.1002/anie.202104677. Epub 2021 Jun 9.

Electrochemical Generation of Hypervalent Bromine(III) Compounds

Igors Sokolovs  1   2 , Nayereh Mohebbati  3   2 , Robert Francke  3   2 , Edgars Suna  1   4
Affiliations

Electrochemical Generation of Hypervalent Bromine(III) Compounds

Igors Sokolovs et al. Angew Chem Int Ed Engl. .

Abstract

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 λ3 -bromanes as well as to their challenging preparation from the highly toxic and corrosive BrF3 precursor. In this context, we present a straightforward and scalable approach to chelation-stabilized λ3 -bromanes by anodic oxidation of parent aryl bromides possessing two coordinating hexafluoro-2-hydroxypropanyl substituents. A series of para-substituted λ3 -bromanes with remarkably high redox potentials spanning a range from 1.86 V to 2.60 V vs. Ag/AgNO3 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 λ3 -bromane activation is exemplified by oxidative C-C, C-N, and C-O bond forming reactions.

Keywords: anodic oxidation; cyclic voltammetry; electrochemistry; hypervalent bromine; oxidative coupling.

PubMed Disclaimer

Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
New approach to aryl‐λ 3‐bromanes.
Figure 2
Figure 2
Synthesis of bromides 2 a–g. [a] Average yield of two runs on 0.3 mmol scale. [b] Yield on 10.0 mmol scale.
Figure 3
Figure 3
Top: Background and iR drop corrected linear sweep voltammograms (LSV) of aryl bromides 2 a–g (c=5 mM) recorded at 10 mV s−1. Bottom: Plot of the half‐peak potentials E P/2 (extracted from the LSVs) vs. the σ p + substituent constants.
Figure 4
Figure 4
Synthetic applications of electrogenerated bromane reagent 3 a.
See this image and copyright information in PMC

References

    1. None
    1. Zhdankin V. V., Hypervalent Iodine Chemistry: Preparation, Structure and Synthetic Applications of Polyvalent Iodine Compounds, Wiley, Chichester, 2013;
    1. Hypervalent Iodine Chemistry; Topics in Current Chemistry, Vol. 373 (Ed.: Wirth T.), Springer International Publishing, Cham, 2016;
    1. Yoshimura A., Zhdankin V. V., Chem. Rev. 2016, 116, 3328–3435. - PubMed
    1. “Oxidative Heterocycle Formation Using Hypervalent Iodine(III) Reagents”: Murarka S., Antonchick A. P., in Hypervalent Iodine Chemistry; Topics in Current Chemistry, Vol. 373 (Ed.: Wirth T.), Springer International Publishing, Cham, 2015, pp. 75–104. - PubMed

LinkOut - more resources