Stefanos Tsitsipas saw his hopes of a hat-trick of titles at the Open 13 Provence ended by a shock quarter-final defeat on Friday.
The second seed was upset by French world number 93 Pierre-Hugues Herbert, as the doubles expert scored a 6-7 (6-8) 6-4 6-2 win.
Herbert had won only one singles match on tour in 2021 before this week, but Kei Nishikori and Cameron Norrie fell to the 29-year-old in the early rounds before he stunned world number five Tsitsipas.
It was a first career win in singles over a player ranked in the world's top five for Herbert, and he said: "It has been an incredible week for me so far, especially this match."
Quoted on the ATP website, Herbert added: "I knew I was going to have to play an amazing match to have a chance to win and I managed to do that. I am really happy about the way I played. I am so happy to be in the semi-finals here."
A French finalist is guaranteed as Herbert will face compatriot Ugo Humbert in the semi-finals on Saturday.
Humbert beat another Frenchman, world number 138 Arthur Rinderknech, in a tight contest, saving a match point and coming through 4-6 7-5 7-6 (7-4) in two hours and 36 minutes.
Russian top seed Daniil Medvedev chased off the threat of Jannik Sinner at this indoor event for the second year running, securing a 6-2 6-4 success against the Italian teenager.
Their only two career meetings have come in Marseille, and Medvedev bossed this encounter, taking three of his five break chances and holding serve throughout.
He will face Australian Matthew Ebden in the final four after the world number 287 earned an eye-catching 4-6 6-4 6-2 win over Russian third seed Karen Khachanov, who was champion in 2018 in Marseille.
At the Qatar Open, Nikoloz Basilashvili backed up his three-set win over Roger Federer by reaching the final of the tournament.
The Georgian scored a 7-6 (7-3) 6-1 semi-final victory over American Taylor Fritz in a clash of two unseeded players.
Basilashvili will tackle Spain's Roberto Bautista Agut for the title on Saturday after the fifth seed ousted Russian third seed Andrey Rublev.
A 6-3 6-3 win for Bautista Agut nudged the man from Castellon de la Plana into a 3-2 career head-to-head lead over his Muscovite opponent.
Canada dump Great Britain out of Davis Cup as Shapovalov, Auger Aliassime win
Canada beat Great Britain to ensure their progress to the Davis Cup Final 8 on Sunday, with Denis Shapovalov beating Dan Evans and Felix Auger Aliassime overcoming Jack Draper.
Canada needed just one point from their final group-stage tie, and Shapovalov did the honours at the first time of asking by beating Evans 6-0 7-5.
Shapovalov won 100% of first-serve points as he dominated an opening set that lasted just 27 minutes, and though Evans came back into the encounter in the second set, a break in the final game sealed the deal for Shapovalov.
With Canada's progress secured, Auger Aliassime then added some gloss by overcoming US Open semi-finalist Draper 7-6 (10-8) 7-5 in a fiercely contested affair.
British pair Neal Skupski and Henry Patten beat Gabriel Diallo and Alexis Galarneau 7-6 (7-4) 6-4 in the doubles, but it was of little consequence with their elimination already certain.
Argentina joined Canada in qualifying from Group D with a sweep of Finland, while Italy finished top of Group A in Bologna, thanks to the efforts of Flavio Cobolli.
He beat Tallon Griekspoor 7-6 (7-4) 4-6 6-3 as the Netherlands were forced to settle for second, after Matteo Berrettini had put the defending champions in the driving seat with a 3-6 6-4 6-4 win against Botic van de Zandschulp.
World number one Jannik Sinner was present to support Berrettini, embracing him after he capped his fightback by converting match point.
Australia and Spain had already sealed qualification from Group B prior to Sunday's matches, while the United States and Germany had clinched their progress from Group C.
The Davis Cup Final 8 will take place in Malaga between November 19 and November 24, with Italy hoping to become the first team to defend the title since the Czech Republic in 2013.
'Not my goal at all' - Djokovic not committing to ATP Finals appearance
Novak Djokovic "can't say" if he will compete in the upcoming ATP Finals in November as he becomes more selective about which tournaments he participates in.
The Serbian has struggled with injuries and a lack of form in 2024, and he will finish a calendar year without a grand slam title for the first time since 2017.
His last major triumph came at the US Open last year, but he failed to defend his crown, suffering a shock early exit to Alexei Popyrin in the third round at Flushing Meadows.
Djokovic is just one grand slam trophy away from becoming the outright record holder, currently sitting level with Margaret Court on 24 titles.
He reached the Wimbledon final in July, only to lose out to Carlos Alcaraz, though he did win his first Olympic gold in Paris by beating the Spaniard the following month.
The 37-year-old is currently representing Serbia at the Davis Cup and stressed that he will be prioritising certain tournaments over others.
"Torino is not my goal at all, to be honest, I am not chasing ATP Finals, I am not chasing the rankings etc," he told Serbian reporters after beating Greece's Ioannis Xilas on Saturday.
"As far as I am concerned, I am done with those tournaments for my career. Whether I will play other tournaments this year or in the future, I can't say right now.
"My main priorities are playing for the national team and slams, everything else is less important.
"Weeks like these represent another motivation, they inspire me to keep going, they awake those butterflies in my belly.
"I thought that I would never have to seek motivation anywhere, it all used to come naturally – automatically – but that has not been the case in the last few years.
"In order to prolong my career, I need to enjoy, I need to choose wisely tournaments I am going to play."
Following the Davis Cup, Djokovic will play in an exhibition tournament in Sofia and in the ATP 1000 event in Shanghai at the start of October.
"After that [Shanghai], I am going to see what I am going to do," Djokovic added.
"Usually in my career I used to have my schedule ready six months in advance, but nowadays, that's not the case. Now it's more spontaneous.
"Firstly, I need to physically, emotionally and mentally rest in order to even start thinking what I want to do next, in what way, how much and where."
Djokovic keeps Serbia on track as Ruud seals Norway win
Novak Djokovic marked his return to action with a dominant 6-0 6-1 victory over Greece's Ioannis Xilas to put Serbia in control of the Davis Cup tie.
The 24-time major winner was playing his first match since his US Open third-round defeat by Alexei Popyrin at Flushing Meadows a fortnight ago.
And Djokovic, who helped his nation win the Davis Cup in 2010, looked close to his best as he dropped just a single game, while converting five of the seven break points he forced.
Wrapping up a dominant victory in just 45 minutes, he put Serbia 2-0 to the good in the World Group I tie.
Elsewhere in that group, Casper Ruud helped Norway wrap up a 3-1 win over Portugal.
The three-time major finalist, who put his nation 2-1 to the good alongside Viktor Durasovic in the doubles rubber, was a 7-6 (7-3) 6-2 victor over Jaime Faria in their singles clash.
Later in the day, Argentina booked their place in the final eight after Maximo Gonzalez and Andres Molteni saw off Finland in the doubles decider.
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