title: Biosynthesis of Shearinine: Diversification of a Tandem Prenyl Moiety of Fungal Indole Diterpenes.
abstract: The late-stage biosynthetic pathway of the indole diterpene shearinine involving four enzymatic reactions (JanQDOJ) was elucidated by an efficient heterologous expression system using Aspergillus oryzae. Key oxidative cyclization, forming a characteristic A/B bicyclic shearinine core by flavoprotein oxidase, was studied using a substrate analogue and a buffer containing H218O. These experimental data provided evidence that JanO catalyzes two-step oxidation via a hydroxylated product and that the JanO reaction involves the hydride-transfer mechanism.
authors.affiliation: Division of Chemistry, Graduate School of Science, Hokkaido University , Sapporo 060-0810, Japan.
authors.forename: Chengwei
authors.initials: C
authors.lastname: Liu
authors.affiliation: Division of Chemistry, Graduate School of Science, Hokkaido University , Sapporo 060-0810, Japan.
authors.forename: Atsushi
authors.initials: A
authors.lastname: Minami
authors.affiliation: Graduate School of Engineering, Hokkaido University , Sapporo 060-8628, Japan.
authors.forename: Tohru
authors.initials: T
authors.lastname: Dairi
authors.affiliation: Graduate School of Agricultural Science, Tohoku University , Sendai 981-8555, Japan.
authors.forename: Katsuya
authors.initials: K
authors.lastname: Gomi
authors.affiliation: Institute of Fundamental Sciences, Massey University , Palmerston North 4442, New Zealand.
authors.forename: Barry
authors.initials: B
authors.lastname: Scott
authors.affiliation: Division of Chemistry, Graduate School of Science, Hokkaido University , Sapporo 060-0810, Japan.
authors.forename: Hideaki
authors.initials: H
authors.lastname: Oikawa
mesh_terms: D001236:Aspergillus oryzae / Q000201:enzymology / Q000235:genetics / Q000378:metabolism*; D053898:Biosynthetic Pathways; D003500:Cyclization; D004224:Diterpenes / Q000378:metabolism*; D005656:Fungal Proteins / Q000235:genetics / Q000378:metabolism; D005800:Genes, Fungal; D006900:Hydroxylation; D026121:Indole Alkaloids / Q000737:chemistry / Q000378:metabolism*; D007211:Indoles / Q000378:metabolism*; D015394:Molecular Structure; D010084:Oxidation-Reduction; D054876:Prenylation
chemical_list: D004224:Diterpenes; D005656:Fungal Proteins; D026121:Indole Alkaloids; D007211:Indoles; C521532:shearinine D