In contrast to the conventional 1,4-addition process, regioselective 1,2-addition of silyl enol ethers to quinones can now be achieved via a palladium(II) enolate pathway that provides access to 4-hydroxy-4-(2-oxo-2-arylethyl)cyclohexa-2,5-dien-1-one derivatives. This quinone alkylation protocol proceeds under mild reaction conditions at ambient temperature under open air and does not require either an external ligand for the palladium or the use of a base. Additionally, the cyclohexadienone products have been exploited as synthetic precursors for the construction of fused heteroaryl systems.