Although mathematicians usually do not work in constructive mathematics per se, their results often are constructively valid (even if the original proof isn't).
An obvious counter-example is the law of excluded middle itself, discovered by Aristotle between 400 and 300 B.C.
LEM is a result in the field of propositional logic. However, what about results outside of logic, like number theory or analysis? The simplest such result I know of is the existence of step functions, but I don't know when that was discovered.
I'll leave "not constructively valid" a bit open-ended, but just saying that there is no known constructive proof doesn't count. A valid answer could show that the result implies a constructive taboo, or that it's independent of a constructive type theory or set theory, for example. (In the case of step functions, their existence implies the analytic LPO, a constructive taboo.)