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Eight arms to hammer on that shield forming a protective cove that Cap can't penetrate. If he catches the shield then it's man to man.

Doc's got 4 arms and his human body which is weak.

But he's still got those 4 arms and I think that's more than enough to take out Captain America. Spiderman usually has his work cut out for him against Doc Ock, and I think Captain America would have more than just his work cut out for him.