I think the point GP was making was to take issue with framing like "and it turning out to be an entirely new class of chemicals."

More accurately we can say "an entirely newly described class of chemicals". Even before penicillin was isolated and described for the first time, soldiers would keep moldy pieces of bread and use them on wounds (Penicillium being the most common bread mold). Even Ötzi the iceman was found to be carrying a piece of fungi that we know was used to kill parasitic worms.

While these traditions didn't conceptualize their medicines as compounds or chemicals, they were certainly well aware of their effects. Sometimes intimately so.

All that aside though, there are bolete species documented to have tryptamine content so I would be a little surprised if the active compound(s) in question here aren't also tryptamines. Although I did read that Dennis McKenna hypothesized it could be an anticholinergic effect (i.e. Datura alkaloids)