Napoli's Gonzalo Higuain grabbed a treble for a 3-1 win over Dynamo Moscow while Kevin de Bruyne's double gave VfL Wolfsburg the same victory over Inter Milan in Europa League last 16, first leg ties on Thursday.
Sevilla midfielder Vitolo recorded the fastest goal ever scored in the competition (13.2 seconds) to lead the holders to a 3-1 triumph at La Liga rivals Villarreal and Fiorentina drew 1-1 with AS Roma in an all-Serie A tie.
Dnipro Dnipropetrovsk beat Ajax Amsterdam 1-0 in Ukraine thanks to Roman Zozulya's goal on the half-hour.
Torino had Marco Benassi sent off in the 28th minute as Zenit St Petersburg won 2-0 in Russia with goals from Axel Witsel and Domenico Criscito on target.
Steven Naismith and Romelu Lukaku, with a penalty, struck in Everton's 2-1 home victory over Dynamo Kiev while Club Bruges also came from behind to beat Besiktas 2-1 in Belgium.
HIGUAIN HAT-TRICK
Kevin Kuranyi headed Dynamo Moscow into a surprise second-minute lead in Naples before the home team equalised when Higuain nodded in a centre from Faouzi Ghoulam.
The Napoli number nine then made it 2-1 from the penalty spot in the 31st minute after Dries Mertens was brought down.
Dynamo had Roman Zobnin sent off one minute into the second half before Higuain completed his treble with a sublime volley, his sixth goal in Europe this season.
Napoli coach Rafa Benitez is aiming to win the Europa League for the second time in three seasons, having guided Chelsea to a 2-1 final victory over Benfica in Amsterdam in 2013.
Triple former European champions Inter went in front against Wolfsburg in Germany when Rodrigo Palacio slipped the ball under keeper Diego Benaglio in the sixth minute.
The hosts, who are second in the Bundesliga, hit back in the 28th when Naldo levelled from a De Bruyne corner.
De Bruyne put Wolfsburg in front with a first-time finish from a Vierinha cross early in the second half before making sure of victory with a curling free kick.
The former Chelsea forward almost made it a hat-trick when he missed an open goal in the closing stages.
"It's a shame," Inter coach Roberto Mancini told reporters. "We knew it was going to be a tough game but we keep giving away cheap goals and in doing so we're making life difficult for ourselves.
"We dropped off too deep after taking the lead, then we left Naldo completely unmarked and let him have a free header two yards from goal."
FASTEST GOAL
At the Madrigal, the ball went forward from the kickoff and Kevin Gameiro set up Vitolo to score a goal that clipped almost two seconds off the previous fastest goal record set by Ismael Blanco of AEK Athens when the competition was launched in 2009.
Stephane M'bia extended Sevilla's lead before Luciano Vietto pulled one back for Villarreal in controversial fashion. M'bia handled the ball in the build-up but the referee allowed the goal to stand, rather than award a penalty, after spending two minutes deliberating with two of his officials.
Gameiro then restored Sevilla's two-goal advantage with a venomous close-range volley in the 50th minute.
Josip Ilicic gave Fiorentina an early lead against AS Roma before the visitors had Adem Ljajic dismissed on the hour. Roma's 10 men fought hard to get back in the tie and they were rewarded when Seydou Keita levelled with 13 minutes to go. The second legs will be played next Thursday.
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