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

ABSTRACT: 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.

SUBMITTER: Mairhofer C

PROVIDER: S-EPMC11228824 | biostudies-literature | 2024

REPOSITORIES: biostudies-literature

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

Mairhofer Christopher C Naderer David D Waser Mario M

Beilstein journal of organic chemistry 20240705

We herein report the oxidative α-azidation of carbonyl compounds by using NaN<sub>3</sub> 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 ...[more]

PMID: 38978746

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