title: Biosynthesis of LL-Z1272β: Discovery of a New Member of NRPS-like Enzymes for Aryl-Aldehyde Formation.
abstract: 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.
authors.affiliation: Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan.
authors.forename: Chang
authors.initials: C
authors.lastname: Li
authors.affiliation: Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan.
authors.forename: Yudai
authors.initials: Y
authors.lastname: Matsuda
authors.affiliation: College of Pharmacy, Jinan University, No.601 Huangpu Avenue, Guangzhou, 510632, China.
authors.forename: Hao
authors.initials: H
authors.lastname: Gao
authors.affiliation: College of Pharmacy, Jinan University, No.601 Huangpu Avenue, Guangzhou, 510632, China.
authors.forename: Dan
authors.initials: D
authors.lastname: Hu
authors.affiliation: College of Pharmacy, Jinan University, No.601 Huangpu Avenue, Guangzhou, 510632, China. tyaoxs@jnu.edu.cn.
authors.forename: Xin Sheng
authors.initials: XS
authors.lastname: Yao
authors.affiliation: Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan. abei@mol.f.u-tokyo.ac.jp.
authors.forename: Ikuro
authors.initials: I
authors.lastname: Abe
mesh_terms: D000447:Aldehydes / Q000737:chemistry; D001230:Aspergillus / Q000201:enzymology / Q000235:genetics; D001547:Benzaldehydes / Q000737:chemistry / Q000378:metabolism*; D002851:Chromatography, High Pressure Liquid; D005810:Multigene Family; D010453:Peptide Synthases / Q000235:genetics / Q000378:metabolism*; D048630:Polyketide Synthases / Q000235:genetics / Q000378:metabolism*; D012717:Sesquiterpenes / Q000737:chemistry / Q000378:metabolism*; D013191:Stachybotrys / Q000737:chemistry / Q000378:metabolism
chemical_list: D000447:Aldehydes; D001547:Benzaldehydes; C000603094:LL-Z1272beta; D012717:Sesquiterpenes; D048630:Polyketide Synthases; D010453:Peptide Synthases; C104385:non-ribosomal peptide synthase
keywords: aryl-aldehyde; biosynthesis; carboxylate reductase; enzymes; meroterpenoids