Chewing coca leafs is healthy and I guess close to impossible to overdose, but if you take a condensed and highly extracted version of that, cocaine, you can very easily overdose.
I heard rumors that in russian prisons people make this condensed coffee drink that acts as a sort of meta-amphetamine replacement. They basically make coffee out of coffee until it's this sticky black thing that gets you really driven, I don't remember what they call it, but I remember many people die from this substance also.
Same thing with natural plant vs chemical extracts. Much easier to overdose and get lethal dosage.