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The widespread presence of bicyclo[1.1.1]pentane (BCP) and sulfur motifs in pharmaceutical compounds underscores the significance of synthesizing suitably functionalized BCP thioethers. In response, we have developed a metal-free and photocatalyst-free strategy that harnesses visible light-induced radical cascades. This approach culminates in the synthesis of essential thio-BCP derivatives, which serve as crucial precursors for the formation of the corresponding sulfoxides, sulfones, and sulfoximines. Importantly, this methodology exhibits potential for large-scale applications, displaying commendable tolerance towards various functional groups while operating under mild reaction conditions.
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