title: Oxidative dearomatisation: the key step of sorbicillinoid biosynthesis†Electronic supplementary information (ESI) available: Containing all experimental details. See DOI: 10.1039/c3sc52911hClick here for additional data file.
abstract: An FAD-dependent monooxygenase encoding gene (SorbC) was cloned fromPenicillium chrysogenumE01-10/3 and expressed as a soluble protein inEscherichia coli. The enzyme efficiently performed the oxidative dearomatisation of sorbicillin and dihydrosorbicillin to give sorbicillinol and dihydrosorbicillinol respectively. Bioinformatic examination of the gene cluster surrounding SorbC indicated the presence of two polyketide synthase (PKS) encoding genes designatedsorbAandsorbB. The genesorbA-encodes a highly reducing iterative PKS while SorbB encodes a non-reducing iterative PKS which features a reductive release domain usually involved in the production of polyketide aldehydes. Using these observations and previously reported results from isotopic feeding experiments a new and simpler biosynthetic route to the sorbicillin class of secondary metabolites is proposed which is consistent with all reported experimental results.
authors.affiliation: School of Chemistry , University of Bristol , Cantock's Close , Bristol BS8 1TS , UK . Email: r.j.cox@bris.ac.uk ; ; Tel: +44 (0) 117 928 9184.
authors.forename: Ahmed Al
authors.initials: AA
authors.lastname: Fahad
authors.affiliation: School of Chemistry , University of Bristol , Cantock's Close , Bristol BS8 1TS , UK . Email: r.j.cox@bris.ac.uk ; ; Tel: +44 (0) 117 928 9184 ; Chemistry of Natural and Microbial Products , National Research Centre , Dokki , Egypt.
authors.forename: Amira
authors.initials: A
authors.lastname: Abood
authors.affiliation: School of Chemistry , University of Bristol , Cantock's Close , Bristol BS8 1TS , UK . Email: r.j.cox@bris.ac.uk ; ; Tel: +44 (0) 117 928 9184.
authors.forename: Katja M
authors.initials: KM
authors.lastname: Fisch
authors.affiliation: School of Chemistry , University of Bristol , Cantock's Close , Bristol BS8 1TS , UK . Email: r.j.cox@bris.ac.uk ; ; Tel: +44 (0) 117 928 9184.
authors.forename: Anna
authors.initials: A
authors.lastname: Osipow
authors.affiliation: School of Chemistry , University of Bristol , Cantock's Close , Bristol BS8 1TS , UK . Email: r.j.cox@bris.ac.uk ; ; Tel: +44 (0) 117 928 9184.
authors.forename: Jack
authors.initials: J
authors.lastname: Davison
authors.affiliation: Institute of Microbiology , Eidgenössische Technische Hochschule (ETH) Zürich , Wolfgang-Pauli-Str. 10 , 8093 Zürich , Switzerland.
authors.forename: Marija
authors.initials: M
authors.lastname: Avramović
authors.affiliation: School of Chemistry , University of Bristol , Cantock's Close , Bristol BS8 1TS , UK . Email: r.j.cox@bris.ac.uk ; ; Tel: +44 (0) 117 928 9184.
authors.forename: Craig P
authors.initials: CP
authors.lastname: Butts
authors.affiliation: Institute of Microbiology , Eidgenössische Technische Hochschule (ETH) Zürich , Wolfgang-Pauli-Str. 10 , 8093 Zürich , Switzerland ; Kekulé Institute of Organic Chemistry and Biochemistry , University of Bonn , Gerhard-Domagk-Str. 1 , 53121 Bonn , Germany.
authors.forename: Jörn
authors.initials: J
authors.lastname: Piel
authors.affiliation: School of Chemistry , University of Bristol , Cantock's Close , Bristol BS8 1TS , UK . Email: r.j.cox@bris.ac.uk ; ; Tel: +44 (0) 117 928 9184.
authors.forename: Thomas J
authors.initials: TJ
authors.lastname: Simpson
authors.affiliation: School of Chemistry , University of Bristol , Cantock's Close , Bristol BS8 1TS , UK . Email: r.j.cox@bris.ac.uk ; ; Tel: +44 (0) 117 928 9184 ; Institut für Organische Chemie , Leibniz Universität Hannover , Schneiderberg 1B , 30167 Hannover , Germany . Email: russell.cox@oci.uni-hannover.de.
authors.forename: Russell J
authors.initials: RJ
authors.lastname: Cox