The cinchona alkaloid quinine promotes the enantioselectivenitroso-aldol reaction between α-aryl-α-cyanoacetates andnitrosobenzene to give the hydroxyamination products withtotal chemoselectivity. Treatment of the reaction mixture withZn/AcOH affords the corresponding amines in high yieldand moderate enantioselectivity. An unusual effect on theenantioselectivity was observed with the catalyst loading andsolvent. A reductive protocol allows the construction of anoptically active 1,2-diamine moiety bearing a quaternarycenter.