Santos claimed an entertaining away win in the Copa Libertadores, while Barcelona clinched a dramatic victory on Wednesday.
A brace from Kayke helped Santos to a 3-2 victory at fellow Brazilian side Atletico Paranaense in the first leg of their last-16 tie.
Atletico had taken a seventh-minute lead at the Estadio Durival de Britto e Silva as Nikao's well-placed effort found the bottom corner from 20 yards.
But Kayke, on loan from Japanese club Yokohama F. Marinos, levelled for the visitors with a good finish after being put through by Lucas Lima in the 25th minute.
Santos took control after the break, but only after some calamitous goalkeeping.
Atletico goalkeeper and Brazil international Weverton somehow spilled what was a tame Victor Ferraz strike from distance, allowing Bruno Henrique to pounce and tap in to make it 2-1.
Santos' third in the 68th minute was far more convincing.
Bruno Henrique turned superbly to make room down the left before crossing for Kayke, who met it with a classy back-heel flick and found the bottom corner.
Ederson pulled a goal back for the hosts four minutes later to give them hope ahead of next month's second leg.
In Guayaquil, Barcelona needed until the 92nd minute to secure a 1-0 win at home to Palmeiras.
Jonathan Alvez struck the winner with some luck, his 30-yard effort taking a huge deflection before rolling into the bottom corner.
Wilstermann claimed a 1-0 victory at home to Atletico Mineiro thanks to Gilbert Alvarez, who scored with an overhead kick in the 41st minute.