Iron-Catalyzed SO2‑Retaining Smiles Rearrangement through Decarboxylation

Radical Smiles rearrangements have emerged as powerful methodologies for constructing carbon–carbon bonds through intramolecular radical addition and fragmentation under milder conditions, with SO2 released as a byproduct. However, SO2-retaining Smiles rearrangements, which can yield valuable alkyl sulfone derivatives, have been scarcely explored. In this study, we present an unprecedented iron-catalyzed SO2-retaining Smiles rearrangement initiated by the decarboxylation of aliphatic carboxylic acids. This approach provides a mild, cost-effective, and versatile pathway to sulfone-containing compounds, demonstrating broad substrate scope and functional group tolerance. It offers a promising strategy for synthesizing γ- and δ-aryl substituted alkyl sulfones, which are traditionally challenging to produce.