Tandem Acylation\nand Aromatization of Vinylogous Esters:\nA Regiospecific Approach to Resorcinyl Ketones

This study demonstrates the direct conversion of vinylogous\nesters\ninto selectively protected 6-acyl resorcinols (4-alkoxy/aryloxy-2-hydroxy\narylketones) in a regiospecific manner. Resorcinyl ketones are first-time\nsynthesized, diverging from their traditional roots, originating from\nnon-benzenoid pool materials. Converting cyclohexenones into phenol-\nor resorcinol-based arylketones remains challenging due to the stability\nand reactivity issues of intermediate products. Addressing this critical\ngap, we introduce a novel strategy: sequential one-pot acylation and\noxidative aromatization of vinylogous esters. This innovative approach\naims to surmount the long-standing barrier, facilitating the synthesis\nof diverse resorcinyl ketones. Furthermore, this method proves valuable\nfor the synthesis of functionalized diaryl ethers and in the total\nsynthesis of bioactive natural products and drug molecules such as\nangolensin, isoliquiritigenin, demethylsorbicillin, ponganone VII,\nand ipriflavone. It is also useful for modifying bioactive acids and\nalcohols by introducing a resorcinol functionality in the late stage\nof synthesis. Synthetic analogues of oxybenzone demonstrated superior\nultraviolet (UV) absorption properties, effectively covering the entire\nUV-A and UV-B regions, spanning from 230 to 410 nm.