Synthetic photochemistry. LXVII. A total synthesis of (±)-hinesol and (±)-agarospirol via retro-benzilic acid rearrangement

Article abstract of DOI:10.1246/bcsj.68.2393

A mild base-catalyzed retro-benzilic acid rearrangement of a proto-photocycloadduct, formed in highly stereoselective photoaddition of methyl 2,4-dioxopentanoate to 1,5-dimethyl-6-methylene-1-cyclohexene, afforded a spiro[4.5]decenedione derivative. Reductive elimination of the α-dicarbonyl function and C₁-homologation furnished (±)-hinesol and (±)-agarospirol.