Department Pharmaceutical Microbiology, Hans-Knöll-Institute, Friedrich-Schiller-Universität, Beutenbergstrasse 11a, 07745, Jena, Germany.
The Usona Institute, 2800 Woods Hollow Road, Madison, WI, 53711, USA.
Chemistry. 2021 Aug 19;27(47):12166-12171. doi: 10.1002/chem.202101382. Epub 2021 Jul 6.
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.
色胺（1）是蘑菇天然产物裸盖菇素去磷酸化和致幻代谢物。1 中 C-4 位酚羟基的氧化导致寡聚吲哚醌发色团的形成，负责挫伤的产裸盖菇素蘑菇的标志性变蓝。基于以前的 NMR 实验，该假设包括 1 的 5,5'-偶联醌二聚体是负责蓝色的主要产物。为了验证该假设，合成了环甲基化的 1 衍生物，以提供 1 二聚体的稳定类似物，这些类似物可以进行完全表征。化学氧化的衍生物进行了光谱分析，并与计算得出的吸收光谱进行了比较。实验证据不支持原始假设。相反，蓝色是由 1 的醌 7,7'-偶联二聚体引起的。
