Cyclopropene activation via I(I)/I(III) catalysis: Proof of principle and application in direct tetrafluorination

Preliminary validation of cyclopropene activation by an I(I)/I(III) catalysis manifold is disclosed to enable the direct tetrafluorination 3,3-diarylcyclopropenes. This transformation occurs through in situ generation ArI(III)F2, with inexpensive iodobenzene, amine·HF complexes and Selectfluor® serving as catalyst, fluoride source oxidant, respectively. Leveraging this approach, it has been possible generate four C(sp3)-F bonds a single operation (up 44%). A Hammett study revealed that reaction very narrow tolerance window respect p-substituent aryl groups. Through process deconstruction, mechanism involving two discrete catalytic processes proposed. Whereas first cycle results ring opening fluorination 3,3-diarylcyclopropene, second proceeds via fluorination/phenonium ion rearrangement liberate tetrafluorinated diarylethane. adds hypervalent iodine plenum strategies facilitate activation.