Despite major advances, intramolecular alkene hydroamination reactions often face limitations. Herein, a redox-enabled process featuring oxidation of an amine to a hydroxylamine, a concerted hydroamination step, followed by catalytic reduction of N-oxide is shown to be broadly applicable. Catalyst screening and optimization showed that a K2OsO2(OH)4-pinacol complex rapidly and chemoselectively reduces the N-oxide cycloadduct in the presence of hydroxylamine and dimethyl sulfoxide. This selectivity was exploited to drive the equilibria toward complex products.