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

IF 2.2 4区化学 Q2 CHEMISTRY, ORGANIC

Beilstein Journal of Organic Chemistry Pub Date : 2024-07-05 DOI:10.3762/bjoc.20.135

Christopher Mairhofer, David Naderer, Mario Waser

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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.

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Beilstein J. Org. Chem. 2024, 20, 1510–1517. doi:10.3762/bjoc.20.135

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叠氮化钠催化四丁基碘化铵对β-酮羰基化合物的氧化α-叠氮反应

摘要我们在此报告在碘化四丁基铵（TBAI）的催化下，在二苯甲酰基过氧化物存在下使用 NaN3 对羰基化合物进行氧化α；-氮化。利用这些现成的大宗化学品，可以在操作简单的条件下高效地 α- 氮化各种环状 β- 酮羰基衍生物。对照实验支持这样一种机理，即在原位形成一种次碘酸铵，首先促进亲核物的 α-碘化，然后在相转移催化下被叠氮化物亲核取代。此外，我们还证明，在其他条件相同的情况下，使用 NaNO2 也可以进行类似的α；-硝化反应。Chem.2024, 20, 1510–1517. doi:10.3762/bjoc.20.135

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来源期刊

Beilstein Journal of Organic Chemistry 化学-有机化学

CiteScore

4.90

自引率

3.70%

发文量

167

审稿时长

1.4 months

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