title: Pyran formation by an atypical CYP-mediated four-electron oxygenation-cyclization cascade in an engineered aureothin pathway.
abstract: Small changes, big effect: A new aureothin derivative, aureopyran, which features an unusual pyran backbone, was generated by simply altering the enzymatic methylation topology. The α-pyrone ring hampers the correct placement of the polyketide backbone in the multifunctional cytochrome P450 monooxygenase AurH. Instead of a tetrahydrofuran ring, an oxo intermediate is formed that readily undergoes a rare electrocyclization reaction.
authors.affiliation: Dept. Biomolecular Chemistry, Leibniz Institute for Natural Product Research and Infection Biology, HKI, Beutenbergstrasse 11a, 07745 Jena, Germany.
authors.forename: Martin
authors.initials: M
authors.lastname: Richter
authors.forename: Benjamin
authors.initials: B
authors.lastname: Busch
authors.forename: Keishi
authors.initials: K
authors.lastname: Ishida
authors.forename: Bradley S
authors.initials: BS
authors.lastname: Moore
authors.forename: Christian
authors.initials: C
authors.lastname: Hertweck
mesh_terms: D002867:Chromones / Q000737:chemistry / Q000378:metabolism*; D003500:Cyclization; D003577:Cytochrome P-450 Enzyme System / Q000378:metabolism*; D004583:Electrons; D008958:Models, Molecular; D010084:Oxidation-Reduction; D011714:Pyrans / Q000737:chemistry / Q000378:metabolism*; D013302:Streptomyces / Q000201:enzymology*
chemical_list: D002867:Chromones; D011714:Pyrans; D003577:Cytochrome P-450 Enzyme System; C012198:aureothin