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Preparation of Stable Bicyclic Aziridinium Ions and Their Ring-Opening for the Synthesis of Azaheterocycles
Published on: August 22, 2018
Tethered Aza-Wacker Cyclization Reactions with Unusual N-Alkoxy Carbamates
Appasaheb K Nirpal1, Dnyaneshwar A Gorve1, Raju Silver1
1Department of Medicinal Chemistry, University of Kansas, Lawrence, Kansas 66047, United States.
Abstract:
Substrates with N-alkoxy carbamate "heads" and olefin "tails" can be productively cyclized into 1,3-oxazinan-2-one products bearing pendant alkenes. Our reaction protocol is operationally simple and involves heating the substrate with a mixture of Pd (II) and Cu (II) salts in CH3CN under 1 atm of O2. We hypothesize that an aza-Wacker mechanism is operative, based on prior art and our own experience with this reaction class. An array of substrates is compatible, and the heterocyclic products are amenable to further transformations.
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