Trapping the elusive aza-oxyallylic cation: new opportunities in heterocycloaddition chemistry

The aza-oxyallylic cation is a reactive intermediate that undergoes a [4+3] cycloaddition with dienes to form seven-membered heterocycles. Although this type of intermediate was proposed over 50 years ago, only recently has experimental evidence been obtained to support its existence. This review highlights the historical studies of aza-oxyallylic cations and their recent development as intermediates for the synthesis of heterocycles and polyheterocyclic scaffolds.