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Well, he should have after seeing it once.
Let's not forget Kakashi knew what Susanoo was even though he never saw it.
He saw the flame. He still doesn't know where it came from or how it works.
To enter SM he summons one boss toad. To take down that boss toad Itachi would have to use either Amaterasu or Susanoo, things he can't spam. Jiraiya has 2 boss toads left to buy more time, and remember Gamaken has a shield.
In this fight he has Tsunade + Katsuyu to help, i seriously doubt they would lose.
@offtopic: Micho22, you should have given location, knowledge, etc. That stuff is always important.
It took Jiraiya a whole chapter just to summon the boss toads. Amaterasu will hit him before any of them are ever summoned. Tsunade can't save him as she can't react to Amaterasu either. So that would just leave Itachi vs Tsunade and its obvious who wins that match up.