Generally, never. Because any small change in chemistry is something that evolution is very effective at picking up. Which means that if there is a simple intervention that improves performance, there is always a good reason why nature hasn't already given it to you. In the case of EPO, it's significantly increased risk of blood clots and blood pressure related conditions.

Caffeine is still the only outlier?

I remain optimistic.

Aspartame seems to be a newer contender