Ganoderma meroterpenoids are fungal derived hybrid natural product class containing a 1,2,4-trisubstituted benzene ring and a polycyclic terpenoid part. The representatives applanatumol E, H and I, lingzhilactone B, and meroapplanin B share the same bicyclic lactone moiety connected to the arene. Employing photo-Fries rearrangements as the key step enabled a general entry to these natural products. For the synthesis of the tetracyclic framework of lingzhiol, we made use of a powerful photoredox oxidative decarboxylation/Friedel-Crafts sequence.

Department of General Inorganic and Theoretical Chemistry University of Innsbruck 6020 Innsbruck Austria

Department of Organic Chemistry and Center for Molecular Biosciences University of Innsbruck 6020 Innsbruck Austria

Department of Organic Chemistry Palacký University Olomouc 77900 Olomouc Czech Republic

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Natural Product Synthesis Enabled by Radical-Polar Crossover Reactions

A General Entry to Ganoderma Meroterpenoids: Synthesis of Applanatumol E, H, and I, Lingzhilactone B, Meroapplanin B, and Lingzhiol