A Redox‐Neutral Organophotocatalytic Cascade: Difluoromethylation and Radical <i>Truce–Smiles</i> ‐Driven C( <i>sp</i> ³ )–H Functionalization to Access Benzothiazine Dioxides and Oxindoles

A new photochemical approach has been developed that enables the simultaneous difluoromethylation and radical cascade cyclization of alkenes, providing rapid and efficient access to structurally intricate 1,2‐benzothiazine dioxide derivatives. Importantly, strategic substrate modification expands the utility of this platform to an unprecedented distal ‘ Radical Truce‐Smiles rearrangement ’ enabled by a 1,5‐hydrogen atom transfer mechanism. This C( sp 3 )–H activation pathway overcomes conventional proximity constraints, allowing for the streamlined synthesis of valuable oxindole frameworks with high selectivity. The organophotocatalyst 4DPNIPN catalyzes the transformation and proceeds via a radical‐polar crossover mechanism initiated through oxidative luminescence quenching. Remarkably, the reaction operates under redox‐neutral conditions, eliminating the need for transition metals, stoichiometric oxidants, or external additives. This sustainable protocol exhibits broad functional group compatibility, operational simplicity, and scalability.