It is an effective punch because the opponent doesn't expect it. However it can leave you open to counters.
You need to have very fast hands and quick reflexes to throw the punch effectively. And Ali had both of the above.
Landing a lead right also gave psychological advantages to him. Basically this is a cheeky shot that boxers throw when in control of a fight as if to say to the opponent 'I am better than you and can do anything in this ring and get away with it'.
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