Cu‐Catalyzed Tetrafluoroethylation of Aryl Iodides Using “Safe Supply” Tetrafluoroethylene

ABSTRACT The success of Cu‐mediated, late‐stage fluoroalkylation, originally developed for CF 3 transfer, has expanded to additional R F groups including C 2 F 5 , CF 2 H, OCF 3, and SCF 3 . Taking advantage of fluoroalkene insertion into Cu‐H or Cu‐F bonds allows for a much broader series of Cu‐R F transfer agents. However, privileged co‐ligands that affect the R F transfer from Cu vary from N‐heterocyclic carbenes, diimines, and even coordinating solvents such as N,N‐dimethylformamide or dimethylsulfoxide. Based on a computational study of ligand effects and several different R F groups, we show that Cu(CF 2 CF 2 H)(PMePh 2 ) 3 —generated from reaction of the stable 1:1 mixture of CO 2 and tetrafluoroethylene (easily obtained by perfluoropropionate thermolysis) with Stryker's reagent, [CuH(PPh 3 )] 6 , and PMePh 2‐ —effects the efficient tetrafluoroethylation of a range of aryl iodides in the presence of catalytic CuCl(SIMes), [SIMes = 1,3‐bis(2,4,6‐trimethylphenyl)‐4,5‐dihydroimidazol‐2‐ylidene].