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Iron-Catalyzed SO<sub>2</sub>-Retaining Smiles Rearrangement through Decarboxylation

Liang Zhang, Yahao Huang, Peng Hu

2024Organic Letters18 citationsDOI

Abstract

Radical Smiles rearrangements have emerged as powerful methodologies for constructing carbon–carbon bonds through intramolecular radical addition and fragmentation under milder conditions, with SO 2 released as a byproduct. However, SO 2 -retaining Smiles rearrangements, which can yield valuable alkyl sulfone derivatives, have been scarcely explored. In this study, we present an unprecedented iron-catalyzed SO 2 -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.

Topics & Concepts

ChemistryDecarboxylationCatalysisSmiles rearrangementMedicinal chemistryStereochemistryOrganic chemistrySulfur-Based Synthesis TechniquesRadical Photochemical ReactionsSynthesis and Catalytic Reactions