Premium
Structural Revision and Elucidation of the Biosynthesis of Hypodoratoxide by 13 C, 13 C COSY NMR Spectroscopy
Author(s) -
Barra Lena,
Ibrom Kerstin,
Dickschat Jeroen S.
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201501765
Subject(s) - stereochemistry , carbon skeleton , biosynthesis , carbon 13 , chemistry , ether , sesquiterpene , nuclear magnetic resonance spectroscopy , metabolite , absolute configuration , terpene , spectroscopy , carbon fibers , organic chemistry , physics , materials science , biochemistry , quantum mechanics , composite number , composite material , enzyme
Feeding of (2,3,4,5,6‐ 13 C 5 )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 C 2 )mevalonolactone, which gave insights into the complex rearrangement of the carbon skeleton during terpene cyclization by analysis of the 13 C, 13 C couplings.