title: Structural Revision and Elucidation of the Biosynthesis of Hypodoratoxide by (13) C,(13) C COSY NMR Spectroscopy.
abstract: Feeding of (2,3,4,5,6-(13) C5 )mevalonolactone to the fungus Hypomyces odoratus resulted in a completely labeled sesquiterpene ether. The connectivity of the carbon atoms was easily deduced from a (13) C,(13) C COSY spectrum, revealing a structure that was different from the previously reported structure of hypodoratoxide, even though the reported (13) C NMR data matched. A structural revision of hypodoratoxide is thus presented. Its absolute configuration was tentatively assigned from its co-metabolite cis-dihydroagarofuran. Its biosynthesis was investigated by feeding of (3-(13) C)- and (4,6-(13) C2 )mevalonolactone, which gave insights into the complex rearrangement of the carbon skeleton during terpene cyclization by analysis of the (13) C,(13) C couplings.
authors: Kekulé-Institut für Organische Chemie und Biochemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Strasse 1, 53121 Bonn (Germany).
authors: Lena
authors: L
authors: Barra
authors: Institut für Organische Chemie, TU Braunschweig, Hagenring 30, 38106 Braunschweig (Germany).
authors: Kerstin
authors: K
authors: Ibrom
authors: Kekulé-Institut für Organische Chemie und Biochemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Strasse 1, 53121 Bonn (Germany). dickschat@uni-bonn.de.
authors: Jeroen S
authors: JS
authors: Dickschat
mesh_terms: D001203:Ascomycota / Q000378:metabolism; D002247:Carbon Isotopes / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008798:Mevalonic Acid / Q000031:analogs & derivatives / Q000737:chemistry / Q000378:metabolism; D008968:Molecular Conformation; D012717:Sesquiterpenes / Q000737:chemistry / Q000378:metabolism*
chemical_list: D002247:Carbon Isotopes; D012717:Sesquiterpenes; C000605189:hypodoratoxide; C015367:mevalonolactone; D008798:Mevalonic Acid
keywords: NMR spectroscopy; biosynthesis; isotopic labeling; structure elucidation; terpenoids