Martin Lang - Studies on the Structure and Biosynthesis of Tridentoquinone and Related Meroterpenoids from Suillus tridentinus

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      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.

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