A general method is described, which allows the overall enantioselective α-alkylation of acyclic ketones in good overall yields (44–86%,, 4 steps) and enantioselectivities ranging routinely from> 94% ee up to virtually complete asymmetric induction (99.5% ee). The acyclic ketones are transformed to their corresponding “SAMP-hydrazones”(S)-2 by reaction with the enantiomerically pure hydrazine (S)-l-amino-2-methoxymethyl-pyrrolidine [SAMP, ...