Palladium-Catalyzed Substrate-Controlled Regiodivergent Hydroamination of gem-Difluoroallenes

We report palladium-catalyzed regiodivergent hydroamination reactions of gem-difluoroallenes. Employing indolines as the nucleophiles leads to the formation of enantioenriched γ-addition products, while the use of 2-indole-carboxylate-type substrates switches the selectivity, delivering β-addition E-alkenes exclusively. This protocol provides efficient access to diverse difluoroalkylated indole derivatives, showing substantial substrate scope and broad functional group compatibility.