Significance The authors describe a zirconium-catalyzed enantioselective hydroamination of alkenes. This is a convenient strategy to access chiral amine building blocks from linear precursors (see Review below). The catalyst system is noteworthy for high reactivity at low temperatures (r.t. or even -30 ˚C), and the observed enantioselectivities are high for hydroamination with unprotected amines.