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

The success of Cu-mediated, late-stage fluoroalkylation, originally developed for CF3 transfer, has expanded to additional RF groups including C2F5, CF2H, OCF3, and SCF3. Taking advantage of fluoroalkene insertion into Cu-H or Cu-F bonds allows for a much broader series of Cu-RF transfer agents. However, privileged co-ligands that affect the RF 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 RF groups, we show that Cu(CF2CF2H)(PMePh2)3—generated from reaction of the stable 1:1 mixture of CO2 and tetrafluoroethylene (easily obtained by perfluoropropionate thermolysis) with Stryker's reagent, [CuH(PPh3)]6, and PMePh2-—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].