Oxidative Ring-Opening Transformation of 5-Acyl-4-pyrones as an Approach for the Tunable Synthesis of Hydroxylated Pyrones and Furans.

A selective and tunable approach for oxidation of 4-pyrones has been developed via ring-opening transformations leading to various hydroxylated oxaheterocycles. The first step of the strategy includes the base-catalyzed epoxidation of 5-acyl-4-pyrones in the presence of hydrogen peroxide for the effective synthesis of pyrone epoxides in high yields. The epoxides bearing the CO 2 Et group are reactive molecules that can undergo both pyrone and oxirane ring-opening via deformylation to produce hydroxylated 2-pyrones or 4-pyrones. The acid-promoted transformation led to 3-hydroxy-4-pyrones (24-76% yields), whereas the K 2 CO 3 -catalyzed ring-opening process of 2-carbethoxy-4-pyrone epoxides proceeded as an attack of alcohol at the C-3 position bearing the CO 2 Et group to give functionalized 6-acyl-5-hydroxy-2-pyrones (27-87% yields). The base-catalyzed reaction of 2-aryl-4-pyrone epoxides was followed by ring contraction and the dearoylation process to produce 3-hydroxyfuran-2-carbaldehydes in 42-80% yields. The transformation of 3-aroylchromone epoxides led to flavonols and 3-hydroxybenzofuran-2-carbaldehyde in the acidic and basic conditions, respectively. The prepared hydroxylated heterocycles demonstrated high reactivity for further transformations and low cytotoxicity and are promising fluorophores or UV filters.