Upcycling Hydrofluorocarbons to Valuable Bis(perfluoroalkyl)carbinols via Nucleophilic Fluoroalkylation

Hydrofluorocarbon (HFC)‐125 (CF 3 CF 2 H) is widely used as a refrigerant; however, its extremely high global warming potential makes it a significant environmental concern. Here, we report a practical strategy to upcycle HFC‐125 into valuable bis(perfluoroalkyl)carbinols, a class of fluorinated alcohols with remarkable acidity and lipophilicity. Optimization studies established efficient conditions for the nucleophilic pentafluoroethylation of trifluoromethyl ketones with HFC‐125, affording octafluorocarbinols in up to 82% yield. A broad substrate scope, including aryl, heteroaryl, and bioactive ketones, was demonstrated. Extension to other HFCs—including HFC‐23, HFC‐329p, and 1H‐heptadecafluorooctane—further expanded the library of highly fluorinated carbinols. Translation to continuous flow synthesis significantly improved efficiency and scalability, delivering higher yields under milder conditions than batch reactions. This work provides a sustainable route to structurally unique, densely fluorinated motifs while addressing the urgent need for recycling high‐global warming potential HFCs.