Abstract: | Selective excited‐state intramolecular proton‐transfer (ESIPT) photocycloaddition of 3‐hydroxyflavones with trans , trans ‐1,4‐diphenyl‐1,3‐butadiene is described. Using this methodology, total syntheses of the natural products (±)‐foveoglin A and (±)‐perviridisin B were accomplished. Enantioselective ESIPT photocycloaddition using TADDOLs as chiral hydrogen‐bonding additives provided access to (+)‐foveoglin A. Mechanistic studies have revealed the possibility for a photoinduced electron‐transfer (PET) pathway. |