Biosynthesis of LL‐Z1272β: Discovery of a New Member of NRPS‐like Enzymes for Aryl‐Aldehyde Formation

LL‐Z1272β ( 1 ) is a prenylated aryl‐aldehyde produced by several fungi; it also serves as a key pathway intermediate for many fungal meroterpenoids. Despite its importance in the biosynthesis of natural products, the molecular basis for the biosynthesis of 1 has yet to be elucidated. Here we identified the biosynthetic gene cluster for 1 from Stachybotrys bisbyi PYH05‐7, and elucidated the biosynthetic route to 1 . The biosynthesis involves a polyketide synthase, a prenyltransferase, and a nonribosomal peptide synthetase (NRPS)‐like enzyme, which is responsible for the generation of the aldehyde functionality. Interestingly, the NRPS‐like enzyme only accepts the farnesylated substrate to catalyze the carboxylate reduction; this represents a new example of a substrate for adenylation domains.