Common Biosynthesis of Non‐Canonical C16 Terpenes through a Fragmentation‐Recombination Mechanism

Abstract

AbstractThe biosynthesis of six recently reported non‐canonical C16 sesquiterpenoids named after ancient Greek philosophers, archimedene, aristotelene, eratosthenene, pythagorene, α‐democritene and anaximandrene, was investigated through density functional theory (DFT) calculations and isotopic labeling experiments. The results revealed for all compounds except archimedene a unique fragmentation‐recombination mechanism as previously demonstrated for sodorifen biosynthesis, in addition to a remarkable “dancing” mechanism for anaximandrene biosynthesis.