@Article{IPB-1139,
author = {Otto, A. and Porzel, A. and Schmidt, J. and Wessjohann, L. and Arnold, N.},
title = {{A study on the biosynthesis of hygrophorone B12 in the mushroom Hygrophorus abieticola reveals an unexpected labelling pattern in the cyclopentenone moiety}},
year = {2015},
pages = {174-180},
journal = {Phytochemistry},
doi = {10.1016/j.phytochem.2015.08.018},
volume = {118},
abstract = {The hitherto unknown natural formation of hygrophorones, antibacterial and antifungal cyclopentenone derivatives from mushrooms, was investigated for hygrophorone B12 in Hygrophorus abieticola Krieglst. ex Gröger \& Bresinsky by feeding experiments in the field using 13C labelled samples of d-glucose and sodium acetate. The incorporation of 13C isotopes was extensively studied using 1D and 2D NMR spectroscopy as well as ESI-HRMS analyses. In the experiment with [U-13C6]-glucose, six different 13C2 labelled isotopomers were observed in the 2D INADEQUATE spectrum due to incorporation of [1,2-13C2]-acetyl-CoA. This labelling pattern demonstrated that hygrophorone B12 is derived from a fatty acid-polyketide route instead of a 1,4-α-d-glucan derived anhydrofructose pathway. The experiment with [2-13C]-acetate revealed an unexpected incorporation pattern in the cyclopentenone functionality of hygrophorone B12. Four single-labelled isotopomers, in particular [1-13C]-, [2-13C]-, [3-13C]-, and [4-13C]-hygrophorone B12, were detected that showed only half enrichment in comparison to the respective labelled alkyl side chain carbons. This labelling pattern indicates the formation of a symmetrical intermediate during hygrophorone B12 biosynthesis. Based on these observations, a biogenetic route via a 4-oxo fatty acid and a chrysotrione B homologue is discussed.}    
}