Well, Rey has challenged for the WWE Title at least once while Brock Lesnar was champ (well, the stip was that if he won he'd get a title shot, but that still kinda counts). I know for a fact that in 1999, he faced Ric Flair for the WCW World Title on an episode of Nitro (which ended in a dq).
Aside from Rey, I can't think of a whole lot of cruisers who have been in World Title matches (not counting ECW and TNA). I know Jeff Hardy faced Undertaker while he was champ, and Hurricane fought Triple H while he was champ, but I don't remember if they were Title matches or not.
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