There are cases of substance that are fine for animals and bad for humans. The fists trials use very small groups and thy have rules like waiting 15 minutes or 1 hour between subjects. There was a very bad disaster a few years ago where the experimenter got lazy and injected everyone almost at the same time and two or tree died and a few had severe health problems.
> miss opportunities
It's totally possible, but if it already killed 50/50 rats, 15/15 dogs and 5/5 monkeys, and they offer me to be the fist human subject, I'd run away faster than Forest Gump.
I imagine there are exceptions. For example, we understand very well why ivermectine kills a lot of invertebrates but not (most) vertebrates and is a very good horse and human dewormer. There may be something that kills everything except humans, and we may understand why theoretically, but I'd not like to be the first to try it.