Andrey Rublev suffered a first-round defeat to Alex de Minaur on a bad day for the big names at the Rotterdam Open.
Second seed Rublev won this event two years ago but there will be no such run this time around after his 6-4 6-4 loss on Wednesday.
De Minaur broke the world number five early in each set and sealed the win at the first time of asking, moving to a 3-0 head-to-head record against Rublev on hard courts.
The Australian will face Maxime Cressy in the next round, who bounced back from his Open Sud de France final defeat by beating Tim van Rijthoven.
Jannik Sinner saw off Cressy in that Montpellier showdown and the Italian carried that form into this tournament, though he needed three sets to overcome Benjamin Bonzi.
Frenchman Bonzi forced a decider but Sinner regained his composure in the final set to prevail 6-2 3-6 6-1 and set up a heavyweight clash with top seed Stefanos Tsitsipas.
There was no such progress for Alexander Zverev, who joined Rublev in suffering an early exit.
The German came unstuck 4-6 6-3 6-4 to home favourite Tallon Griekspoor, whose four wins over top-20 opponents have all come in Rotterdam.
Stan Wawrinka, the champion in 2015 and runner-up four years later, will face the winner of that tie, after he beat Richard Gasquet 6-3 6-3 to reach the quarter-finals.
Holger Rune reached the semi-finals in Montpellier, and like Sinner the fourth seed progressed into round two, claiming a routine straight-sets victory over qualifier Constant Lestienne.
"It was tricky. It's a lot about finding the rhythm here in the beginning of the tournament and first match you have to really be on your toes, especially I played a qualifier today who already has two matches in his bag," Rune said.
"It made it more difficult, but I'm happy how I handled every situation today."
Hubert Hurkacz was another seed to fall out, with the world number 10 going down 7-6 (7-4) 7-6 (7-5) to Grigor Dimitrov.
Swiatek seals Italian Open hat-trick after soaring past Sabalenka
Iga Swiatek stormed to her third Italian Open title following a dominant 6-2 6-3 victory over Aryna Sabalenka.
The world number one took just under an hour-and-a-half to deny the world number two, and complete a hat-trick of triumphs in Rome.
The pair were contesting a second final in as many events, with Swiatek saving three championship points before eventually prevailing in the Madrid Open showpiece a fortnight ago.
However, it was one-way traffic this time around. The Pole converted two out of three break points as she controlled the opening set.
Sabalenka was the last player to deny Swiatek in a WTA final, that coming at last year's Madrid Open.
Although, the second seed was helpless as her opponent broke again in game seven of the second set, before wrapping up a fourth title of the season ahead of the French Open later this month.
Data debrief
Landing her third Italian Open title before turning 23, Swiatek is only the second player to achieve that feat after Gabriela Sabatini.
In fact, at 22 years and 352 days old, she is the youngest player to win 10 WTA 1000 titles since the introduction of the format in 2009.
The Pole also became the third player to triumph in Madrid and Rome during the same season, after Dinara Safina (2009) and Serena Williams (2013).
Jarry defeats Paul to set up Zverev showdown in Italian Open final
Nicolas Jarry defeated Tommy Paul in three sets on Friday to set up a showdown with Alexander Zverev in the Italian Open final.
The men's world number 24 prevailed 6-3 6-7 (3-7) 6-3 in a little under three hours in Rome to reach his first ATP Masters 1000 final.
Jarry earned the only break of serve in the eighth game of the opening set, but Paul - who dropped just one set in four matches en route to this stage - hit back in the second.
Birthday boy Paul lost serve to trail 4-2 at one stage, but he produced one of the shots of the tournament at the ideal moment and soon dragged it back to 4-4.
A gruelling set concluded with Paul taking the tie-break 7-3, but Jarry was unperturbed and won the deciding set with his fifth match point to see off Paul in a gruelling contest.
Data Debrief:
Jarry is the third male Chilean in the Open Era to reach the singles final of the Italian Open after Marcelo Rios (1997-98) and Fernando Gonzalez (2007).
The 28-year-old registered 13 aces against Paul to his opponent's seven and hit 35 winners to 19 in a deserved victory.
Zverev ends Tabilo's dream run to reach Italian Open final
Alexander Zverev fought back from the brink to reach the Italian Open final on Friday, overcoming Alejandro Tabilo by a 1-6 7-6 (7-4) 6-2 scoreline in the last four.
Zverev was punished for a slow start as Tabilo took the opener within 32 minutes, but the German fought back in a one-hour, 15-minute slog of a second set.
The 2017 Italian Open champion put his foot down from 3-3 in the second-set tie-break, with Tabilo potentially feeling the effects of a fine run that included a last-32 upset of Novak Djokovic.
Zverev upped the intensity in the final set and won a huge 94 per cent of points behind his first serve as his opponent wilted, the third seed reaching the Rome final for a third time.
Data Debrief: Zverev draws level with Becker
Zverev will now face either Nicolas Jarry or Tommy Paul in Sunday's final, which will be his 11th at ATP 1000 Masters level.
That tally pulls him level with Boris Becker for most such finals by a German player since the format's 1990 introduction.
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