Publication Details (including relevant citation information):
Martin Lang, Andrea Mühlbauer, Claudia Gräf, Jürgen Beyer, Susanne Lang-Fugmann, Kurt Polborn, Wolfgang Steglich
Eur. J. Org. Chem. 2008, 816-25
Tridentoquinone, the main pigment of Suillus tridentinus is accompanied by the known meroterpenoid bolegrevilol and a dimer, tridentorubin. The absolute configuration of tridentoquinone was unambiguously established by a single-crystal X-ray analysis of the corresponding (–)-camphanoate. The structure of tridentorubin was elucidated by 2D NMR techniques including a 2D INADEQUATE experiment.
Feeding experiments with [1-13C]-labeled 4-hydroxybenzoic acid and 3,4-dihydroxybenzoic acid proved the incorporation of these precursors into all three metabolites. Tridentoquinone was monolabeled at C-1 suggesting the formation of the ansa ring by oxidative cyclisation of 2-geranylgeranyl-6-hydroxybenzoquinone. This was supported by the isolation of the expected intermediate, deoxytridentoquinone, from the mushroom extract.
Tridentorubin may be formed by addition of a precursor to tridentoquinone. This hypothesis is backed up by the in vitro formation of an analogous product from tridentoquinone and 1,4-benzoquinone.
Address (URL): http://dx.doi.org/10.1002/ejoc.200700908