I think Mir did - versus Sylvia, versus Lesnar, and versus JDS. If you count interim title shots, he has two more (Nog and Carwin).
I believe Faber had three shots at the FW title (winning one) and then at BW he had two shots at the undisputed title and one at the interim title.
GSP had two shots at Hughes and his rematch with Serra, plus an interim shot at Hughes.
I think BJ has had four shots at the LW title.
Off the top of my head, that's all I can think of.
I like Cain and I think he has a good chance of winning a rematch despite the first fight being a blowout, but he should have had to win at least one more first, imo. This shot should be AA's. (Which, interestingly, I think would be AA's third shot.)