The thermomorphic BINAP derivative 1 tagged with long alkyl chains was prepared from (S)-5,5'-diamino BINAP and applied to Ru-catalyzed asymmetric hydrogenation of beta-ketoesters under homogeneous conditions in 3:1 (v/v) ethanol/1,4-dioxane at 60 degrees C with high enantioselectivity (up to 98% ee). Results indicated that the Ru(1) catalyst was easily recovered by simple cooling and precipitation and could be used for at least four cycles without any loss of enantioselectivity.