The match also marked the first time a deciding set was played at this year's tournament as Fritz bounced back from a set down with a dominant display in the second before running away with the third set.
US Open runner-up Fritz can qualify for the final-four if Sinner takes a set in his match against Medvedev. But the American will be eliminated if Medvedev beats Sinner in straight sets.
Seventh seed De Minaur, meanwhile, goes home without winning a single match in the Ilie Nastase group on his tournament debut.