N, N'-Acetals are sensitive compounds, and the challenging asymmetric synthesis of acyclic N, N'-acetals by the general addition of amines to ketimines has never been reported so far. In this study, highly enantioselective addition of aryl amines to isatin-derived ketimines catalyzed by chiral urea derived from quinine was developed. A series of new acyclic N, N'-acetals were constructed by this protocol in high to excellent yields (78-99%) and high to excellent enantioselectivities (76-96% ee).