Fridays Child, a prewarp society with pretty rocks, no PD.
PD probably suspended because of Organian Peace Treaty. Unless you feel the Klingons are entitled to do the cultural damage of the indigenous society while the UFP is not.
Horta Planet, a prewarp society (after the eggs hatch) with pretty rocks, no PD.
Regardless how the PD would deal with non-humanoid sentient beings, it was obvious that they didn't know that they were dealing with a lifeform.
Mirror Mirror, were the Halkons prewarp? Anyway no PD.
You could probably add the indigenous societies from "A Private Little War" and "The Omega Glory".
This just illustrates why I usually don't like this retroactive continuity BS. Suddenly "prewarp" status has become the benchmark by which to retroactively judge whether our TOS protagonists did violate the PD or not.
I hope I'm not the only one who considers that the TOS producers had something other than this "prewarp" stuff in mind. Spock's concerns in "Errand of Mercy" suggested that the UFP considered the impact on a medieval society as considerate.
Other than that, contact between Starfleet personnel and "prewarp" indigenous cultures wasn't prohibited by the TOS era PD per se
The major issue was not to reveal superior technology to a less advanced culture. This became clear in "A Piece of the Action" (transtater field equipment forgotten by McCoy), "A Private Little War" ("use of our phasers is expressly forbidden") and "The Omega Glory" ("Interesting that the villagers know about phasers.").
Kirk's log entry in "The Omega Glory" follows Spock's observation (there's not much else they learned in the short amount of time):
"A growing belief that Captain Tracey has been interfering with the evolution of life on this planet. It seems impossible. A star captain's most solemn oath is that he will give his life, even his entire crew, rather than violate the Prime Directive."
Put simply, the TOS PD wasn't about "prewarp" but about concealing phaser or superior technology in general.