Late‐Stage Photocatalytic Fluoroalkylation of Aromatic Crown Ethers in Aqueous Media

Modified crown ethers are fundamental building blocks in supramolecular chemistry, with applications in phase transfer catalysis, metal extraction, smart materials, and molecular machines. Here we report on a one-pot highly chemo- and regioselective photocatalytic fluoroalkylation protocol for the mono-functionalization of benzo substituted crown ethers. For this important class of macrocycles, the method described here represents one of the few late-stage functionalization procedures that is both high yielding and scalable. Because of its breadth of scope and substrate tolerance, the devised approach can be applied to a wide range of aromatic crown ethers (18 examples, up to 99 % yield), including those engaged in mechanically interlocked molecules.