Photoredox catalysis has developed into a powerful tool for the synthesis of organic compounds with diverse structures. However, stable carbon–chloride bonds remain beyond the energetic limits of the outer-sphere photoreductive activation. Here, we demonstrate that the organization of the reacting species in microstructured, aqueous solutions allows generation of carbon-centred radicals from non-activated alkyl chlorides in the presence of double bonds via assembly-promoted single electron transfer. Photocatalytic systems consisting of a surfactant, organic substrates and additives have been designed, characterized and applied for radical dechlorination, addition and cyclization reactions. Cheap and commercially available blue light-emitting diodes are used as the irradiation source for the transformations. Mechanistic studies indicate the accumulation of the energy of two visible light photons in one catalytic cycle.

光氧化还原催化已发展成为合成具有不同结构的有机化合物的强大工具。但是，稳定的碳-氯键仍然超出了外层光还原活化的能量极限。在这里，我们证明了在微结构的水溶液中反应物种的组织允许通过组装促进的单电子转移，在双键存在的情况下从非活化的烷基氯生成以碳为中心的自由基。由表面活性剂，有机底物和添加剂组成的光催化体系已被设计，表征并应用于自由基脱氯，加成和环化反应。廉价且可商购的蓝色发光二极管用作转换的辐照源。