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Preparation of Stable Bicyclic Aziridinium Ions and Their Ring-Opening for the Synthesis of Azaheterocycles
Published on: August 22, 2018
Practical azidation of 1,3-dicarbonyls
Tobias Harschneck1, Sara Hummel, Stefan F Kirsch
1Department of Chemistry, Technische Universität München, Lichtenbergstr. 4, 85747 Garching, Germany.
A new method simplifies the direct azidation of 1,3-dicarbonyl compounds using sodium azide and iodine oxidants. This approach provides a novel route to valuable azido compounds and complex molecule analogues.
Area of Science:
- Organic Chemistry
- Synthetic Chemistry
Background:
- 1,3-Dicarbonyl compounds are versatile synthetic intermediates.
- Traditional methods for azidation of these compounds can be challenging and limited in scope.
Purpose of the Study:
- To develop a simple and direct method for the azidation of 1,3-dicarbonyl compounds.
- To explore the utility of iodine-based oxidants for this transformation.
- To synthesize novel tertiary 2-azido and 2,2-bisazido 1,3-dicarbonyl compounds.
Main Methods:
- Direct azidation of 1,3-dicarbonyl compounds using sodium azide.
- Employing iodine-based oxidants, specifically I(2) or 2-iodoxybenzoic acid (IBX)-SO(3)K/NaI.
- Reaction conditions conducted under ambient temperature.
Main Results:
- Successful development of an operationally simple, direct azidation protocol.
- The IBX-SO(3)K/NaI system demonstrated excellent functional group tolerance and substrate scope.
- Access to a variety of tertiary 2-azido and 2,2-bisazido 1,3-dicarbonyl compounds was achieved.
- Azide-containing products readily underwent 1,3-dipolar cycloaddition with alkynes.
Conclusions:
- The developed method offers a novel and efficient route to azido-functionalized 1,3-dicarbonyl compounds.
- This approach facilitates the synthesis of analogues of sensitive complex molecules.
- The use of IBX-SO(3)K/NaI as an oxidizing agent is highlighted for its effectiveness and broad applicability.
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