Electrocyclizations of N-Vinylnitrones and [3,3’]-Sigmatropic Rearrangement of N,O-Divinylhydroxylamines

Our research group has developed new transformations involving N-vinylnitrone and N,O-divinylhydroxylamine intermediates to facilitate the synthesis of functionalized molecules and to access novel heterocyclic structures. Recently, we have expanded the scope of these methods to include the synthesis of oxazine-N-oxides through the 6π-electrocyclization of transient N-vinylnitrones, azetidine N-oxides through 4π-electrocyclization of N-vinylnitrones and the preparation of N-furanylamides through the addition of N,O-divinylhydroxylamines to electron-deficient allenes. The optimization, scope, and limitations of these new transformations will be discussed to emphasize new fundamental reactivity patterns and a detailed description of the synthetic versatility of these heterocyclic products will be presented to illustrate their utility in facilitating the preparation of sophisticated structures.