Russian 2017 finalist Rublev was outclassed by De Minaur on Wednesday but bounced back 24 hours later, following the Australian through from Group B.
Winless wildcard Liam Caruana went down 4-3 (9-7) 4-1 4-2 to leave Rublev far more satisfied with his performance as he approaches a semi-final against Tsitsipas.
“This was a completely different performance,” he said. “My attitude, I think, was the best attitude out of these three matches.
“I was focused. I was not complaining. I was trying to fight for every point because I know that every point for me costs a lot. I was just trying to win each point, every point, doesn’t matter the score.”
De Minaur was similarly dominant as he won his third straight match in Milan after a shaky first set, defeating Taylor Fritz 4-3 (10-8) 4-1 4-2.
“I’m really proud of my effort and I’m looking forward to what’s next,” De Minaur said.
And Munar completed the last-four line-up as the already-qualified Tsitsipas beat Hubert Hurkacz 4-1 4-3 (7-2) 4-1 in the day’s late game.
Hurkacz still had the opportunity to progress ahead of that clash, but he was blown away and Munar - who ended Frances Tiafoe’s hopes earlier on Thursday - instead went through.
Munar had joked after a rampant 4-1 4-3 (7-3) 4-1 triumph: “I did what I had to do and it’s not in my hands anymore. Maybe we can buy a Greek flag or whatever for support.”
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