Amination and Para ‐C─H Arylation of Aryl Fluorides Enabled by α‐Methylnaphthyl (MeNAP) Palladium Catalysts

Abstract The C─F bond is among the strongest in organic molecules and can be cleaved only by few transition metal catalysts under harsh conditions or with highly reactive nucleophiles. We herein report that a methyl naphthyl (MeNAP) palladium bromide / BrettPhos catalyst with lithium bis(trimethylsilyl)amide (LiHMDS) as the base promotes aminations of non‐activated aryl fluorides already at 40–60 °C to give primary, secondary, and tertiary anilines. A related catalyst system further enables para ‐C─H arylations of tritylated anilines with aryl fluorides, yielding biarylamines.