Tandem catalysis enables chlorine-containing waste as chlorination reagents.

Chlorinated compounds are ubiquitous. However, accumulation of chlorine-containing waste has a negative impact on human health and the environment due to the inapplicability of common disposal methods, such as landfill and incineration. Here we report a sustainable approach to valorize chlorine-containing hydrocarbon waste, including solids (chlorinated polymers) and liquids (chlorinated solvents), based on copper and palladium catalysts with a NaNO promoter. In the process, waste is oxidized to release the chlorine in the presence of N-directing arenes to afford valuable aryl chlorides, such as the FDA-approved drug vismodegib. The remaining hydrocarbon component is mineralized to afford CO, CO and HO. Moreover, the CO and CO generated could be further utilized directly. Thus, chlorine-containing hydrocarbon waste, including mixed waste, can serve as chlorination reagents that neither generate hazardous by-products nor involve specialty chlorination reagents. This tandem catalytic approach represents a promising method for the viable management of a wide and diverse range of chlorine-containing hydrocarbon wastes.