The addition of aluminium alkyls to terminal olefins leads to branched organoaluminium compounds which can be converted into functionalised alkanes. This carboalumination reaction is efficiently catalysed by a donor functionalised Cp-chromium(III) complex. The active catalyst is obtained by activation of the chromium(III) dichloride precursor with MAO or with a mixture of trialkylaluminium and N,N-dimethylanilinium tetrakispentaflourphenylborate. Primary aminoalkenes deactivate the catalyst whereas secondary and tertiary aminoalkenes can also be carboaluminated.