Systematic changes in the substitution pattern of linear enones (R1COCH CHR2) helps identify the reactive conformation (s-trans versus s-cis) of the enone in copper-catalysed asymmetric 1, 4-ZnEt2 addition. Pointers to the binding mode of the Lewis Acid (syn or anti to the 'ene'function) are also gathered. Enantioselectivities of up to 79% have been realised in these reactions.