text: In 1941, Kharash discovered that Grignard reagents add to cyclohexenone in presence of Cu(I) resulting in 1,4-addition instead of 1,2-addition.  This work foreshadowed extensive studies on the conjugate additions to enones with organocuprates. Note that if a Grignard reagent (such as RMgBr) is used, the reaction with an enone would instead proceed through a 1,2-addition. The 1,4-addition mechanism of cuprates to enones goes through the nucleophilic addition of the Cu(I) species at the beta-carbon of the alkene to form a Cu(III) intermediate, followed by reductive elimination of Cu(I). In the original paper describing this reaction, methylmagnesium bromide is reacted with isophorone with and without 1 mole percent of added copper(I) chloride (see figure).
  Without added salt the main products are alcohol B (42%) from nucleophilic addition to the carbonyl group and diene C (48%) as its dehydration reaction product. With added salt the main product is 1,4-adduct A (82%) with some C (7%).
  A 1,6-addition is also possible, for example in one step of the commercial-scale production of fulvestrant: