Oxovanadium(V) compounds induce nucleophilic alpha,beta-vicinal dialkylation of cyclic alpha,beta-enones with dialkylzinc reagents. Alkylzinc enolates generated from cyclic enones and lithium trialkylzincates were also oxidized by VO(OEt)Cl(2), giving 2, 3-dialkylcycloalkanones.