Our interest in the development of transition-metal catalysis for the realisation of vicinal diamination reactions of alkenes started about a decade ago. A number of successful transformations in this area have been developed using palladium catalysis. As a challenging aspect of major importance, the palladium-catalysed coupling of alkyl–nitrogen bonds constitutes the second step in diaminations of alkenes. We here discuss the details that led us to consider high-oxidation-state palladium catalysis as a key feature in such C–N bond-forming reactions. This work discusses both our own contributions and the ones from colleagues and combines the discussion of catalytic reactions and stoichiometric control experiments. It demonstrates that reductive alkyl–nitrogen bond formation from palladium(IV) proceeds with a low activation barrier and through a linear transition state of nucleophilic displacement.