Tetrabutylammonium Iodide-Catalyzed Oxidative α-Azidation of β-Ketocarbonyl Compounds Using Sodium Azide

Submitting author affiliation:
Johannes Kepler University Linz, Linz, Austria

Beilstein Arch. 2024, 202420. https://doi.org/10.3762/bxiv.2024.20.v1

Published 02 Apr 2024

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We herein report the oxidative α-azidation of carbonyl compounds by using NaN3 in the presence of dibenzoylperoxide catalyzed by tetrabutylammonium iodide (TBAI). By utilizing these readily available bulk chemicals a variety of cyclic β-ketocarbonyl derivatives can be efficiently α-azidated under operationally simple conditions. Control experiments support a mechanistic scenario involving in situ formation of an ammonium hypoiodite species which first facilitates the α-iodination of the pronucleophile, followed by a phase-transfer catalyzed nucleophilic substitution by the azide. Furthermore, we also show that an analogous α-nitration by using NaNO2 under otherwise identical conditions is possible as well.

Keywords: Organocatalysis; quaternary ammonium iodides; oxidation; azidation; nitration

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When a peer-reviewed version of this preprint is available, this information will be updated in the information box above. If no peer-reviewed version is available, please cite this preprint using the following information:

Mairhofer, C.; Naderer, D.; Waser, M. Beilstein Arch. 2024, 202420. doi:10.3762/bxiv.2024.20.v1

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