Beilstein Journal of Organic Chemistry (Jul 2024)

Tetrabutylammonium iodide-catalyzed oxidative α-azidation of β-ketocarbonyl compounds using sodium azide

  • Christopher Mairhofer,
  • David Naderer,
  • Mario Waser

DOI
https://doi.org/10.3762/bjoc.20.135
Journal volume & issue
Vol. 20, no. 1
pp. 1510 – 1517

Abstract

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We herein report the oxidative α-azidation of carbonyl compounds by using NaN3 in the presence of dibenzoyl peroxide 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.

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