Significance Gold nanoclusters (mean size: 1.3 nm) stabilized by poly( N -vinyl-2-pyrrolidone) (Au/PVP) was applied to the intramolecular hydroamination of primary amines. Thus, the hydroamination of the primary amine 1a was performed with Au/PVP (5 atm%) under the conditions C to give 2a (94% yield), 3a (2% yield), and 4a (4% yield).