Direct Access to 3,4,6-Trisubstituted 2-Pyrones via Carbene Catalysis.

An N -heterocyclic carbene-catalyzed [4 + 2] annulation of β,γ-unsaturated α-keto esters and phenylacetate esters was developed for the direct and efficient construction of 2-pyrones. This approach provides a practical synthesis pathway for various 3,4,6-trisubstituted 2-pyrones in moderate to good yields and features broad substrate scope and good functional group tolerance. Moreover, the products can also be readily transformed to naphthalene and acylamide.