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

The biosynthesis of six recently reported non‐canonical C 16 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.