Nature Catalysis, Published online: 20 August 2026; doi:10.1038/s41929-026-01581-0 The catalytic formation of C–N bonds remains a central challenge in synthetic chemistry owing to the widespread occurrence of amine motifs in pharmaceuticals, agrochemicals, and other bioactive compounds. By merging photoredox and phosphine catalysis, researchers extend the reactivity of P(IV) intermediates to π-systems, enabling the Markovnikov-selective hydroamination of terminal alkenes and redefining the scope of main-group catalysis.