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.
PubMed ID: 31725937
Publication type: Journal
Journal: Angew Chem Int Ed Engl
Citation: Angew Chem Int Ed Engl. 2020 Jan 20;59(4):1450-1454. doi: 10.1002/anie.201910175. Epub 2019 Dec 4.
Date Published: 20th Jan 2020
Registered Mode: by PubMed ID
Created: 10th May 2021 at 14:00