The palladium-induced cleavage of β-ketosters and enol carbonates derived from α-alkylated 1-indanones and 1-tetralones in the presence of (+)-endo-2-hydroxy-endo-3-aminobornane led to (R)-α-alkylated indanones and tetralones with a large increase in the enantioselectivity (up to 38-40%) when the reaction temperature was raised from 21 to 45-70°C. Thus, enantiopure 2-methyl-1-indanone was obtained at 52°C. More than one inversion temperature has appeared in plotting the corresponding Eyring diagrams.