The enantioselective carboalumination of alkenes leads to asymmetric carbon-carbon bond formation. Upon oxidation of the resulting aluminum alkyls, chiral primary alcohols may be obtained. The rate constants for dissociation of the relevant heterobimetallic species, [L₂Zr(μ-R)AlR₂]⁺, were measured by magnetization transfer. Based on the magnitude of the dissociation rate constant, promising catalysts were identified for use in the asymmetric carboalumination of olefins. The ability of various enantiopure zirconocenes to catalyze the asymmetric methylalumination and ethylalumination of allylbenzene has been tested. The observed enantioselectivity in methylalumination using an ethylenebis(indenyl)zirconium dichloride/MAO ((EBI)ZrCl₂/MAO) system is the same as that of the authentic methyl cation generated with trityl cation from (EBI)ZrMe₂, thus confirming that the methyl cation is the active catalyst from the (EBI)ZrCl₂/MAO system.