Structure Elucidation and Spectroscopic Analysis of Chromophores Produced by Oxidative Psilocin Dimerization
Chemistry - A European Journal – June 01, 2021
Source: OpenAlex
Summary
The iconic blue hue of psilocybin mushrooms, a natural product central to psychedelics and drug studies, has been precisely identified. Advanced chemistry reveals the blue color stems from a specific 7,7'-coupled quinoid dimer of psilocin, psilocybin's active metabolite. Previous assumptions pointed to a 5,5'-coupled dimer. Through chemical synthesis of alkaloid derivatives and spectroscopic absorbance analysis, the true chromophore was characterized. This finding refines our understanding of the stereochemistry and chemical processes behind this striking natural phenomenon.
Abstract
Abstract Psilocin ( 1 ) is the dephosphorylated and psychotropic metabolite of the mushroom natural product psilocybin. Oxidation of the phenolic hydroxy group at the C‐4 position of 1 results in formation of oligomeric indoloquinoid chromophores responsible for the iconic blueing of bruised psilocybin‐producing mushrooms. Based on previous NMR experiments, the hypothesis included that the 5,5’‐coupled quinone dimer of 1 was the primary product responsible for the blue color. To test this hypothesis, ring‐methylated 1 derivatives were synthesized to provide stable analogs of 1 dimers that could be completely characterized. The chemically oxidized derivatives were spectroscopically analyzed and compared to computationally derived absorbance spectra. Experimental evidence did not support the original hypothesis. Rather, the blue color was shown to stem from the quinoid 7,7’‐coupled dimer of 1 .