title: Experimental and Theoretical Studies on Corvol Ether Biosynthesis.
abstract: The biosynthesis of corvol ethers A and B, two sesquiterpenes from Kitasatospora setae, proceeds with involvement of either one 1,3- or two sequential 1,2-hydride shifts. Quantum chemical calculations revealed that the sequence of two 1,2-hydride shifts is energetically favoured. Labelling experiments were in agreement with this finding. In addition, the stereochemical course of a reprotonation step was investigated by incubation of (13)C-labelled isotopomers of farnesyl diphosphate in water and in deuterium oxide.
authors.affiliation: Kekulé-Institut für Organische Chemie und Biochemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Strasse 1, 53121, Bonn, Germany.
authors.forename: Patrick
authors.initials: P
authors.lastname: Rabe
authors.affiliation: Kekulé-Institut für Organische Chemie und Biochemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Strasse 1, 53121, Bonn, Germany.
authors.forename: Aron
authors.initials: A
authors.lastname: Janusko
authors.affiliation: Department für Chemie, Universität zu Köln, Greinstrasse 4, 50939, Köln, Germany.
authors.forename: Bernd
authors.initials: B
authors.lastname: Goldfuss
authors.affiliation: Kekulé-Institut für Organische Chemie und Biochemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Strasse 1, 53121, Bonn, Germany. dickschat@uni-bonn.de.
authors.forename: Jeroen S
authors.initials: JS
authors.lastname: Dickschat
mesh_terms: D003511:Cyclohexanols / Q000737:chemistry; D004987:Ethers / Q000138:chemical synthesis* / Q000737:chemistry; D000077591:Eucalyptol; D009682:Magnetic Resonance Spectroscopy; D008962:Models, Theoretical; D015394:Molecular Structure; D039821:Monoterpenes / Q000737:chemistry; D027544:Salvia; D012717:Sesquiterpenes / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D003511:Cyclohexanols; D004987:Ethers; D039821:Monoterpenes; D012717:Sesquiterpenes; D000077591:Eucalyptol
keywords: NMR spectroscopy; isotopic labeling; quantum chemical calculations; reaction mechanisms; terpene biosynthesis