Iron-Catalyzed\nSO<sub>2</sub>‑Retaining Smiles\nRearrangement through Decarboxylation

Radical Smiles rearrangements have\nemerged as powerful methodologies\nfor constructing carbon–carbon bonds through intramolecular\nradical addition and fragmentation under milder conditions, with SO<sub>2</sub> released as a byproduct. However, SO<sub>2</sub>-retaining\nSmiles rearrangements, which can yield valuable alkyl sulfone derivatives,\nhave been scarcely explored. In this study, we present an unprecedented\niron-catalyzed SO<sub>2</sub>-retaining Smiles rearrangement initiated\nby the decarboxylation of aliphatic carboxylic acids. This approach\nprovides a mild, cost-effective, and versatile pathway to sulfone-containing\ncompounds, demonstrating broad substrate scope and functional group\ntolerance. It offers a promising strategy for synthesizing γ-\nand δ-aryl substituted alkyl sulfones, which are traditionally\nchallenging to produce.