Organophotocatalysis: Insights into the Mechanistic Aspects of Thiourea‐Mediated Intermolecular [2+2] Photocycloadditions

Abstract

AbstractMechanistic investigations of the intermolecular [2+2] photocycloaddition of coumarin with tetramethylethylene mediated by thiourea catalysts reveal that the reaction is enabled by a combination of minimized aggregation, enhanced intersystem crossing, and altered excited‐state lifetime(s). These results clarify how the excited‐state reactivity can be manipulated through catalyst–substrate interactions and reveal a third mechanistic pathway for thiourea‐mediated organo‐photocatalysis.