Liverpool fell 2-1 at Union Saint-Gilloise in their final Europa League group game on Thursday, while Villarreal knocked Rennes out of the competition with a thrilling win in France.
Azeri club Qarabag advanced to the knock-out round, while Slavia Prague finished first in Group G, ahead of last season’s runners-up Roma.
With his club already secured as Group E winners and an eye on the weekend’s Premier League encounter against rivals Manchester United, Liverpool manager Jurgen Klopp made six changes, starting six players aged 20 or younger.
Saint-Gilloise, who needed a win to keep their hopes of beating Toulouse to second place alive, took the lead through Mohamed Amoura before Liverpool’s Jarell Quansah equalized.
Cameron Puertas restored the hosts’ lead with a low strike that beat Caoimhin Kelleher at his near post two minutes before halftime.
Klopp introduced Joe Gomez, Ryan Gravenberch, and Darwin Nunez in the second half, but Saint-Gilloise held on for a famous win, but the Belgians were eliminated from the Europa Conference League play-off round because Toulouse defeated LASK Linz 2-1 in the group’s other game.
With a 3-2 victory over Rennes, Villarreal clinched first place in Group F and straight qualification to the last 16.
Lorenz Assignon scored in the 12th minute of injury time to bring Rennes back to the top of the group, but his goal was ruled out by VAR, and scuffles erupted after the final whistle.
The Ligue 1 club merely needed to avoid defeat to finish first, but instead will face a team that has already been eliminated from the Champions League in the play-off.
Qarabag finished second in Group H after defeating Haecken 2-1.
They were still eight points behind group winners Bayer Leverkusen, who thrashed Molde 5-1 to extend their unbeaten start to the season to 23 matches in all competitions.
Despite overcoming Sheriff Tiraspol 3-0, Jose Mourinho’s Roma had to settle for a knock-out play-off berth as Slavia Prague thrashed Servette 4-0.
Aston Villa qualified for the last 16 of the Conference League as Nicolo Zaniolo scored his first goal for the club in a 1-1 draw at Bosnian club Zrinjski.