Emerging Trends in Organic Photoreactions Utilizing Disulfides

The facile photolysis of the sulfur‐sulfur bond in disulfides has emerged as a powerful and versatile strategy in organic chemistry. This review surveys the rapidly growing field of disulfide‐mediated photoreactions, including both catalytic and cocatalytic systems, as well as their roles across homogeneous and developing heterogeneous platforms. We highlight how electronically tuned disulfides function as photoactivated thiyl‐radical precursors and, in many cases, as bifunctional radical mediators that enable hydrogen‐atom transfer (HAT), electron shuttling, and polarity‐matched radical trapping. Representative reaction classes include anti‐Markovnikov hydrofunctionalizations of alkenes, oxidative alkene oxygenation and CC cleavage, hydrophosphinylation, hydrofluoroalkylation, decarboxylative transformations, C(sp 3 )–H functionalizations, and alkene/alkyne isomerizations. The review discusses the strategies for translating molecular disulfide chemistry into recyclable heterogeneous materials and polymer‐supported catalysts. The photochemical flexibility and tunability of disulfides through electronic modification, combined with their commercial availability and low toxicity, position them as attractive alternatives to expensive precious‐metal photoredox catalysts for advancing industrially viable and sustainable photochemistry.