Very recently (2024), a photoinduced cascade sulfone alkylation/cyclization of 2-isocyanoaryl thioethers 61 was demonstrated (Scheme 21) . This visible-light-driven reaction occurs under exceptionally mild conditions without requiring a photosensitizer. The process is initiated by the formation of an EDA complex A between (2-isocyanophenyl)(methyl)sulfane and α-iodosulfone 62. Upon visible-light irradiation, this complex generates radical cation B⁺ • , a sulfone methyl radical C (TsCH₂ • ), and an iodine anion. Quinuclidine is oxidized by B⁺ • to form a quinuclidinium radical cation, while the sulfone methyl radical C adds to the 2-isocyanoaryl thioether to produce imidoyl radical D. This intermediate undergoes intramolecular cyclization, yielding sulfonium radical E. Two possible pathways then emerge. In the first pathway, E releases a methyl radical, forming the target product 63 (R 1 = H, R 2 = 4-tolyl) alongside a by-product. In the second pathway, E is oxidized by the quinuclidinium radical cation to form sulfonium cation F. A subsequent nucleophilic attack by iodine anion on F generates the desired product 63 and methyl iodide, which reacts with quinuclidine to form quaternary ammonium salt G. Scheme 21. EDA complex catalyzed synthesis of benzothiazoles 63.