The first catalytic enantioselective conjugate addition of alkylboron compounds has been achieved. Reactions between alkylboranes and imidazol-2-yl alpha,beta-unsaturated ketones proceeded with high enantioselectivity under the influence of a Cu(I) catalyst system, prepared in situ from CuCl, a new chiral imidazolium salt as a precursor for the N-heterocyclic carbene ligand, and PhOK. Alkylboranes are widely obtained via alkene hydroboration. A variety of functional groups are tolerated in alkylboranes and alpha,beta-unsaturated ketones.