The enantioselective and intermolecular addition of nucleophiles to internal olefins is a challenging process due to the typically low reactivity of these substrates. Hydroaminations of 1,4-disubstituted dienes present further challenges as several product regioisomers may be obtained and reactions tend to be reversible, leading to erosion of enantiopurity of products over time. The Malcolmson lab has now demonstrated that Pd–PHOX catalysts facilitate the regio- and enantioselective hydroamination of internal dienes with aliphatic amines and anilines. A series of experiments shed light on the reaction mechanism, elucidating the reversibility of individual steps of the catalytic cycle as well as the reaction as a whole. Read more about this research here in ACS Catalysis.