Nature Communications, Published online: 20 June 2026; doi:10.1038/s41467-026-74595-8 The authors report a regioselective hydrogen atom transfer process that enables divergent carbamoylation of branched alkenes. Through modulation of the electronic and steric properties of the ligands, this cobalt complex achieves precise discrimination between hydrogen atoms exhibiting minor differences in bond dissociation energies (BDEs), affording vinyl and allylic amides with predictable selectivity.