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Tom Cruise (Iron Man)
Tom Cruise (Iron Man)

Blending narcissistic comedy with gritty pathos, Robert Downey Jr. was the perfect casting choice for Iron Man, but RDJ came after a string of other A-listers to get the role that put him back in Hollywood's good graces. For a while, it seemed like pretty much a lock that billionaire playboy turned tech-enhanced superhero Tony Stark would be portrayed by none other than Tom Cruise. And more than just star, Cruise was planning to produce and develop the the film as well. But as time went on Cruise lost interest in the project and steered clear when the movie actually started getting made.

Hugh Jackman (Iron Man)
Hugh Jackman (Iron Man)

Though he was already widely known for playing another Marvel hero, Hugh Jackman was also a candidate to portray Tony Stark. Since Fox owns the rights to Jackman's X-Men movies, his character of Wolverine is actually not considered to be a part of the Marvel Cinematic Universe. Ultimately, Robert Downey Jr. wound up being chosen over Jackman, which was probably for the best given that his own string of Wolverine and X-Men movies would start up just a year later.

Emily Blunt (Black Widow)
Emily Blunt (Black Widow)

Before Scarlett Johansson slipped into that black jumpsuit to become the deadly spy Natasha Romanoff, the role was meant for Emily Blunt. At the time, Blunt had just started breaking big in Hollywood following her scene-stealing supporting role in The Devil Wears Prada a couple years earlier, and said that scheduling conflicts were to blame for her being unable to take the part that was offered to her.

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