Asymmetric hydrogenation of isoquinolines is still one of the important challenges that remain unmet. In an activated N-benzyl isoquinolinium form, the isoqunolines substrates can be smoothly hydrogenated with excellent activity and enantioselectivity and the value of ee is up to 96%. This substrate activation not only destroys the aromaticity of isoquinoline to enhance the reactivity but also efficiently avoid the coordination between catalyst and substrates. Besides, the poison effect of amine product wou...