Photoinduced Synthesis of α-Aryl-β-arylthiopropanamide from N-(Arylsulfonyl)methacrylamide via Smiles Rearrangement.

We report a photoinduced, sulfur-radical-mediated Smiles rearrangement for the mild and operationally simple synthesis of α-aryl-β-arylthiopropanamide derivatives. This method requires no external photocatalysts or oxidants and offers a straightforward and efficient route to these compounds bearing quaternary carbon centers and arylthio groups. Mechanistic studies indicate that the sulfur radicals are mainly generated through an energy transfer (EnT) pathway, underscoring the distinctive feature of this approach.