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Preparation of Stable Bicyclic Aziridinium Ions and Their Ring-Opening for the Synthesis of Azaheterocycles
Published on: August 22, 2018
Formal [1,5] Rearrangement of Cyclopropanone Hemiaminals: Synthesis of Tetrahydrobenzazepinone Derivatives
Zack R Ferrin1, Vincent N G Lindsay1
1Department of Chemistry, North Carolina State University, 2620 Yarbrough Drive, Raleigh, North Carolina 27695, United States.
Abstract:
A convergent synthetic approach to the formation of tetrahydrobenzazepin-2-ones from 2-aminobenzaldehyde derivatives and cyclopropanone surrogates is reported. In this process, a stable hemiaminal intermediate spontaneously rearranges at room temperature upon generation of a remote iminium species, via a concerted and diastereoselective ring opening/homo-Mannich pathway occurring through a boat transition state. Such a formal [1,5] rearrangement of cyclopropanone hemiaminals is unprecedented and thus represents a novel strategy for the elaboration of seven-membered heterocyclic compounds.
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