On the matter of "A list characters". . . being major important characters in the comics is utterly meaningless. What matters is public exposure and pop culture awareness. So, yes, prior to 2001, the only A list character Marvel had, in the sense of being at all comparable to Superman or Batman? Spider-man. I'm comfortable adding "Wolverine" after the X-Men movies came out and made him an icon ( and bumped him out of the B-list he was already on ).
Prior to the MCU, the Hulk had a reasonably well-remembered 70s TV show, a couple of cartoons over the years, and one fairly unsuccessful movie. Iron Man. . . had a couple cartoons that were at best as prominent as the Hulk's cartoons, and that's it. Thus, Hulk was B-list ( the average person actually knows about him, and can probably name a few facts ), and Iron Man was. . . not ( the average person likely doesn't even know his name ).
Compare that with Spider-man, who even prior to 2001, had numerous fairly long running and successful cartoons, a few 70s TV and movie stuff, and a generally high level of pop culture awareness such that the average person could not only describe several important facts about the character, but likely could sing the whole Spider-man theme song. And then proceeded to gain massive attention the moment a movie was actually happening, to record-breaking success.
And even that looks fairly small compared to Superman and Batman. By 2001, Superman had 4 movies ( and a spinoff ), three live actions TV shows, and numerous cartoons. Batman had four ( or five! ) movies, one live action TV show, and more cartoons than you could shake a stick at, including actual Emmy Awards. Both characters, the average man on the street could not only name most of the important facts about them, but also run down a list of important supporting characters for both. Their *sidekicks and love interests* are iconic in a way that nobody at Marvel save Spider-man was.
Marvel has several A-list characters right now, who have jumped ahead and are now major pop culture icons. Its important not to confuse this modern case with the way things once were. Just because Iron Man is an A-list icon now, doesn't mean he wasn't a non-entity prior to RDJ.
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