UEFA Champions League
Benfica midfielder Beto (right) celebrates after scoring the decisive goal with teammate Nuno Gomes.
Benfica, who began the day bottom of the group, grew in confidence and took the lead with a deflected Beto shot after 34 minutes.
Despite dominating possession after the break, United never really looked likely to grab an equaliser that would have been good enough to send them through after the Villarreal result.
"It's a big success, this is not an experienced Benfica team said victorious coach Ronald Koeman.
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