Harry Kane scored twice in his first league appearance in front of a home crowd to steer champions Bayern Munich to a 3-1 victory over Augsburg.
After a tense encounter finished 1-1 following extra time, Villareal's Rulli stepped up after every on-field player scored their spot kicks and he comfortably beat Spaniard De Gea
Spain face Ronald Koeman's Netherlands away on Thursday before returning home for the second-leg on March 23.
Liverpool survived a first-half scare to reach the Champions League final with a 3-2 win at Villarreal on Tuesday that secured a 5-2 aggregate victory after the night had threatened to turn sour for Juergen Klopp's side.
The home side knew only victory would do for them to grab the final last-16 qualification spot in the group behind Manchester United, and came out for the second half in all-out-attack mode.
An own goal and a Sadio Mane strike earned Liverpool a 2-0 victory in their Champions League semi-final first-leg against Villarreal on Wednesday, putting Juergen Klopp's side on course for their third European Cup final in five seasons.
Goals in each half from Kai Havertz and Christian Pulisic earned defending champions Chelsea a solid 2-0 first-leg victory over Lille in the Champions League last 16 on Tuesday.
Villarreal's struggles in the Spanish league continued with a 2-1 loss at Athletic Bilbao, with striker Gerard Moreno not finishing the game because of an injury.
Real Madrid saw off a stirring Chelsea fightback to book their place in the Champions League semi-finals following a 3-2 defeat after extra time in a scintillating second leg at the Santiago Bernabeu on Tuesday to go through 5-4 on aggregate.
Karim Benzema's hat-trick earned Real Madrid a 3-1 win at reigning European champions Chelsea in their Champions League quarter-final first leg on Wednesday. In another quarter-final match, Villarreal stunned six times European Cup winners Bayern Munich 1-0.
Barcelona bounced back from their painful Clasico loss in style as they cruised to a 3-0 home LaLiga win over Villarreal with a brace from Robert Lewandowski on Thursday.
Holders Chelsea made light of their off-pitch problems to reach the Champions League quarter-finals by beating Lille 2-1 away on Wednesday to complete a 4-1 aggregate victory.
A summary of Saturday's action in the LaLiga, Serie A and Bundesliga.
Spanish soccer clubs Villarreal and Getafe have denied any wrongdoing after national media reported on Friday that police are investigating possible match-fixing in a 2-2 draw between the two clubs in La Liga last year. Newspaper El Pais reported that the match was being looked at as part of Operation Oikos, which was launched last year and led to 11 people being arrested on suspicion of forming a match-fixing group to profit from betting on games.
Unai Emery's Villarreal were much improved in the second half and had spurned numerous chances before Moreno's leveller.
Barcelona and Villarreal failed to put the pressure on leaders Real Madrid as they dropped points in the Primera Liga.
IMAGES from the football matches played across Europe on Sunday.
Central defender Eric Bailly joined Manchester United from Spanish side Villarreal on a four-year contract with the option to extend for a further two years, the Premier League club said on Wednesday.
Leicester keeper Schmeichel defends under-fire De Gea
All the action from La Liga and Serie A matches played on Monday
Cristiano Ronaldo and Gareth Bale both scored as Real Madrid staged a remarkable late comeback from two goals down to win 3-2 at Villarreal and stay top of La Liga.
Marco Ruben's header put Villarreal up to third in La Liga with a 1-0 win at Athletic Bilbao on Sunday, after Valencia fell to a solitary Ivan Rakitic strike in a pulsating encounter with Sevilla.
La Liga club Villarreal have been given Real Mallorca's place in this season's Europa League pending a Mallorca appeal.
Athletic Bilbao missed a chance to tighten their grip on Spain's fourth Champions League qualification place when they had to come from behind to rescue a 1-1 draw at 10-man Villarreal in La Liga on Monday.
Valencia will meet Olympique Marseille in the UEFA Cup final after a 1-0 aggregate win over Villarreal.
Images from La Liga matches played on Monday.
Villarreal romped to a 5-0 home victory over promoted Tenerife on Sunday, continuing their revival after a poor start to the La Liga campaign.
Villarreal and Atletico Madrid continued to struggle in La Liga after both slumped to unexpected defeats on Sunday.
A summary of Wednesday night's action in the UEFA Champions League.
Villarreal secured their place in the Champions League qualifying round with a 2-0 win at local rivals Valencia on Sunday, guaranteeing fourth place in La Liga.
Real Madrid have avoided defeat in their last 41 LaLiga games, the second best streak by a team in the competition's history.
In-form Luciano Vietto hit two second half goals as Villarreal, down to 10 men for the final 10 minutes, cruised to a 3-0 home victory over Deportivo La Coruna to go fifth in La Liga.
Kylian Mbappe bagged his first hat-trick for Real Madrid as the LaLiga champions easily beat bottom-club Real Valladolid 3-0 on Saturday
Villarreal's slide continued as a Diego Castro header gave Getafe a 1-1 draw in La Liga on Sunday but the match was overshadowed by a serious injury to Mateo Musacchio.
Inter Milan grabbed a slender advantage over Villarreal with a 2-1 comeback win the in Champions League first-leg quarter-final
Twice in arrears Rangers earned a 2-2 home draw with Villarreal
AC Milan sneaked through to the semi-finals, beating Olympique Lyon 3-1 in the other second leg quarter-final with two late goals. Inter were eliminated on the 'away goals' rule.
The 45-year-old former striker, a 2010 World Cup semi-finalist, has switched to tennis since his retirement in 2018, playing on the international senior tour.
