Palladium‐Catalyzed Fluorinative Bifunctionalization of Aziridines and Azetidines with gem‐Difluorocyclopropanes

Abstract An unprecedented Pd‐catalyzed fluorinative bifunctionalization of aziridines and azetidines was successfully developed via regioselective C−C and C−F bond cleavage of gem‐difluorocyclopropanes, leading to various β,β′‐bisfluorinated amines and β,γ‐bisfluorinated amines. This reaction was achieved by incorporating a 2‐fluorinated allyl group and a fluorine atom scissored from gem‐difluorocyclopropane in 100 % atom economy for the first time. The mechanistic investigations indicated that the reaction underwent amine attacking 2‐fluorinated allyl palladium complex to generate η 2 ‐coordinated N‐allyl aziridine followed by fluoride ligand transfer affording the final β‐ and γ‐fluorinated amines.