Yes. For a while, you could buy beta-phenyl-GABA in a mass-market grocery store here, right off the shelf. It sounds relatively harmless, but beta-phenyl-GABA is a flat-out synthetic GABA-B agonist [1] developed in Russia in the 1960s. It works similarly to the prescription drug Baclofen. It can cause physical dependence, and has a potentially-life-threatening withdrawal syndrome similar to that of alcohol or benzodiazepines.
When it comes to things labelled as "dietary supplements" in the US, the FDA is more-or-less asleep at the wheel IMO.
[1] Edit: I'm wrong, it's apparently a https://en.wikipedia.org/wiki/Gabapentinoid like gabapentin and the DEA Schedule V drug pregabalin.