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It was Mbappe's first game as team captain after Hugo Lloris announced his international retirement and the Paris St Germain forward led by example while keeper Mike Maignan saved a late penalty in a flawless performance.
Coach Christophe Galtier's star-studded team that includes striker Kylian Mbappe and world champion Lionel Messi failed to score against Bayern over two legs, losing 3-0 on aggregate.
Argentina scooped all major men's awards after winning a vintage World Cup final last December.
Brahim Diaz's goal gave AC Milan a 1-0 win over Tottenham Hotspur in their last-16 first leg at the San Siro.
Messi could win his second The Best trophy after leading Argentina to their third World Cup title by beating Mbappe's France in last year's final in Qatar, scoring seven goals during the tournament and earning his second Golden ball.
Midtable Reims extended its unbeaten run to 12 games, which included holding PSG to a 0-0 draw at home in October, and was the better side in the first half.
The legendary actor was invited to Riyadh as the chief guest for the star-studded football match between Paris St Germain and All-star XI.
In an action-packed first half at the King Fahd Stadium in Riyadh, goals from Messi and Marquinhos were cancelled out by a Ronaldo brace.
Scaloni also revealed that he prioritised speaking to Messi when he was named Argentina coach in 2018, while the forward was taking a break from international duty following the disastrous World Cup in Russia.
Lionel Messi, along with his PSG teammate Kylian Mbappe and Manchester City's Erling Haaland, were among the 14 players shortlisted for The Best FIFA Men's Player award.