Different from lithium dialkylcuprates, Cu(II) catalyzed conjugate addition of Grignard reagents to allylic esters of alpha,beta-unsaturated carboxylates has been effected in the presence of TMS-Cl, and the resulting allyl silyl keteneacetals further undergo rearrangement to afford 2-alkyl 3-alkyl carboxylic acids in good yields.