Palladium‐Initiated Radical Cascade Stereoselective Iodofluoroalkylation/Cycloisomerization of Ene‐vinylidenecyclopropanes

A novel and convenient palladium-initiated radical cascade stereoselective iodofluoroalkylation/cycloisomerization of ene-vinylidenecyclopropanes with fluoroalkyl iodides has been developed. The reaction proceeds under mild reaction conditions with high atom economy and stereoselectivity, thereby allowing an efficient access to a variety of difluoromethylated or perfluoroalkylated pyrrolidines tethered with an alkyl iodide. Two plausible radical pathways for the transformation have been proposed on the basis of the results of control experiments and previous reports, which in one case it was thought that palladium(0) was an initiator rather than a catalyst.