Department Pharmaceutical Microbiology, Hans-Knöll-Institute Friedrich-Schiller-Universität, Beutenbergstr. 11a, 07745, Jena, Germany.
Synthetic Microbiology, Friedrich-Schiller-Universität, Leibniz Institute for Natural Product Research and Infection Biology – Hans-Knöll-Institute, Winzerlaer Str. 2, 07745, Jena, Germany.
Department Biomolecular Chemistry, Leibniz, Institute for Natural Product Research and Infection Biology -, Hans-Knöll-Institute, Beutenbergstr. 11a, 07745, Jena, Germany.
Upon injury, psychotropic psilocybin-producing mushrooms instantly develop an intense blue color, the chemical basis and mode of formation of which has remained elusive. We report two enzymes from Psilocybe cubensis that carry out a two-step cascade to prepare psilocybin for oxidative oligomerization that leads to blue products. The phosphatase PsiP removes the 4-O-phosphate group to yield psilocin, while PsiL oxidizes its 4-hydroxy group. The PsiL reaction was monitored by in situ 13 C NMR spectroscopy, which indicated that oxidative coupling of psilocyl residues occurs primarily via C-5. MS and IR spectroscopy indicated the formation of a heterogeneous mixture of preferentially psilocyl 3- to 13-mers and suggest multiple oligomerization routes, depending on oxidative power and substrate concentration. The results also imply that phosphate ester of psilocybin serves a reversible protective function.
© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
enzymes; laccase; natural products; phosphatase; psilocybinPMID: 31725937 DOI: 10.1002/anie.201910175