This report describes a carboxylate-assisted palladium-catalysed Catellani reaction, which is compatible with ortho-amination and unactivated C(sp²)–H arylation. This method was used to synthesize a series of 1-amino substituted dihydrophenanthridines, phenanthridines and 6H-benzo[c]chromenes. Based on kinetic isotope experiments, the kinetic curve proves that pivalic acid accelerates the reaction rate of unactivated C(sp²)–H activation, and thus this rate can keep up with the five membered aryl-norbornene–palladacycle (ANP) intermediate.