Institute of Organic Chemistry
and Biochemistry of the CAS

Merging rearrangement with radical reactions is a largely unexplored field but may hold promise for approaching scaffolds that are inaccessible by other methodology. Here a tandem nucleophilic substitution/Brook rearrangement/single‐electron transfer oxidation/radical oxygenation strategy is presented, through which α,γ‐dioxygenated ε,ζ‐unsaturated amides are efficiently prepared in a single step from enantiomerically enriched allylepoxides and 2‐silylacetamides. The resulting compounds can be easily transformed by persistent radical effect‐based 5‐exo‐trig or 6‐endo‐trig radical cyclization reactions to functionalized carbocycles bearing three or four stereocenters. The stereochemical outcome of the cyclization reactions can predicted by the Beckwith–Houk model. The cyclic compounds can be easily diversified by post‐cyclization modifications. The tandem process can be further extended by an acylation step leading to β‐dicarbonyl enolates, which were also transformed to cyclopentane and cyclohexane derivatives under oxidative conditions.