Tandem anionic oxy-Cope rearrangement/radical oxygenation reactions provide delta,epsilon-unsaturated alpha-(aminoxy) carbonyl compounds, which serve as convenient precursors to diverse compound classes. Functionalized carbocycles are accessible by very rare all-carbon 5-endo-trig cyclizations, but also common 5-exo-trig radical cyclizations, based on the persistent radical effect.
The tandem reactions can be further extended by highly diastereoselective allylation or reduction steps to give complex scaffolds.