Abstract
AbstractAn 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 η2‐coordinated N‐allyl aziridine followed by fluoride ligand transfer affording the final β‐ and γ‐fluorinated amines.
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