Controllable Double Difluoromethylene Insertions into S−Cu Bonds: (Arylthio)tetrafluoroethylation of Aryl Iodides with TMSCF₂Br

Abstract

A n ew method of constructing “ArSCF2CF2Cu” from ArSCu and TMSCF2Br (TMS = trimethylsilyl) has been developed. The cross‐coupling reactions of the obtained “ArSCF2CF2Cu” with diverse aryl iodides provide an efficient access to Ar’CF2CF2SAr. Mechanistic studies demonstrate that the “ArSCF2CF2Cu” species w ere generated through controllable double difluoromethylene insertions into ArS ‐ Cu bond rather than the 1,2‐addition to tetrafluoroethylene.