Biosynthesis of (−)‐Vinigrol

(−)‐Vinigrol, as one of the most complex and challenging molecules in total synthesis, the parallel biosynthetic strategy employed by nature for the synthesis of this compound has not yet been identified. Here, we identified a minimal gene cluster encoding a diterpene cyclase (VniA) and a cytochrome P450 (VniB), which completes the synthesis of (−)‐vinigrol through three steps. VniA first cyclizes geranylgeranyl diphosphate to generate an unusual vinigrol‐type diterpene skeleton, and then VniB catalyzes the allylic C(sp3)‐H iterative oxidation. Further genome mining investigation provides new fungal sources for this rare and valuable vinigrol‐type diterpene skeleton.