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 η2 -coordinated N-allyl aziridine followed by fluoride ligand transfer affording the final β- and γ-fluorinated amines.
Keywords: Aziridines; Fluorination; Gem-Difluorocyclopropane; Ring Opening; β-Fluorinated Amines.
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