Radical initiation for the perfluoroalkylation reaction of amino(hetero)aromatics has been accomplished employing the complex [(TMEDA)I$I 3 ] and visible light. This methodology circumvents the use of metal(organo)catalysts and biologically-relevant substrates are easily substituted with R F moieties employing a mild and environmentally benign radical strategy starting from readily-available perfluoroalkyl iodides R F I.

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.