Smiles rearrangement enables the migration and structural reorganization of aromatic rings, providing an efficient strategy for the construction of tetrasubstituted alkenes. Despite significant advances, examples of Smiles rearrangements involving inert propargylamines remain limited owing to restricted substrate availability and inherent reactivity challenges. Herein, we report a photocatalyst-free photochemical radical Smiles rearrangement of N-sulfonylpropargylamines via 1,4-N-to-C aryl migration, affording valuable polysubstituted allylamines with high stereoselectivity. Notably, the resulting sulfur-containing tetrasubstituted allylamines exhibit pronounced aggregation-induced emission (AIE) properties, highlighting their potential in organic synthesis and advanced materials science.
Zhang et al. (Fri,) studied this question.