The umpolung of β,γ-unsaturated diketones through N-heterocyclic carbene catalysis is described, which allows access to a variety of highly functionalized bicyclic cyclohexene-β-lactones and 1,3,4-triaryl benzenes. An unprecedented reaction pattern involving the catalytic formation of nucleophilic O-acylated homoenolate intermediate is proposed. A diverse set of transformations on the product further showed the synthetic potential of this protocol.