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A superb last-ditch tackle from Rooney upended David Ousted, and the former Manchester United star then launched a long ball into the area met by Luciano Acosta, who nodded home the winner.
Mourinho surprisingly put Pogba straight into the starting line-up and handed him the armband even though the Frenchman had just returned to training on Monday.
Less than a month since Pogba scored in the World Cup final to help France lift the trophy, he was thrown straight into action by Mourinho against Leicester City.
Despite adding two centre-backs on deadline day for Premier League clubs, Leicester also resisted interest from Manchester United for England international Harry Maguire.
Sanchez is the biggest star of Chilean football and the epitome of a rags to riches success story.
For the first time the Premier League deadline was moved forward to the day before the season kicks off when United host Leicester City on Friday.
Manchester United aim to defy manager Jose Mourinho's doubts in Premier League opener against Leicester
Mourinho has repeatedly called for more backing in the transfer market if United are to close the record 19-point gap they trailed Manchester City by last season despite finishing second in the table.
The 31-year-old eight-time Olympic champion, who retired from athletics last year, is an avid Manchester United fan who has long wanted to play top-flight football.
Mourinho has expressed his frustration over the club's transfer policy, and Pogba's departure would leave little time for executive chairman Ed Woodward to find a suitable replacement.
United's build-up to the new campaign has been dominated by manager Jose Mourinho's persistent grumbles over the strength of his squad.