Tetrafluoroethylation of Electron‐Rich Alkenyl Iodides Enabled by in situ Generation of Solvent‐Stabilized “Ligandless” CuCF₂CF₂H

In this study, we have developed a metal‐mediated synthetic method for incorporating the 1,1,2,2‐tetrafluoroethyl (CF 2 CF 2 H) motif into unactivated, electron‐rich alkenyl iodides using cross‐coupling reactions. We discovered that the stable Cu(CF 2 CF 2 H)(PPh 2 Me) 3 complex, while unreactive with these substrates, serves as a P‐ligated reservoir for the formation of solvent‐stabilized “ligandless” and reactive CuCF 2 CF 2 H species. This transformation occurs upon addition of CuBr, which partially scavenges the P‐ligand in the form of CuBr(PPh 2 Me) 3 . The resulting in situ generated solvent stabilized “ligandless” system significantly enhances the reactivity of the complex, particularly towards challenging electron‐rich substrates. This advancement enables the synthesis of HCF 2 CF 2 ‐glycals, as well as nucleosides/nucleobases and arenes.