Manchester City were the last side to inflict a defeat on United, with Kevin De Bruyne inspiring them to a 2-1 win in September of past year.
The eight Champions League Round of 16 ties take place over four days.
Stephan El Shaarawy warned Roma to ignore Chelsea-Atletico Madrid and focus only on Qarabag.
Juve join Group D winners Barcelona, who rounded off their group phase with a routine 2-0 win at home against Sporting Lisbon.
Manchester United will qualify in top spot if they draw against CSKA Moscow at Old Trafford tonight.
Benfica are yet to pick up a single point and will therefore finish bottom of the group no matter what happens on Tuesday.
Powered by a front three of Neymar, Edinson Cavani and Kylian Mbappe, PSG had set a group-stage record of 24 goals before kick-off at the Allianz Arena, but were comfortably seen off by the five-time champions despite holding on to seal top spot in Group B. Juventus will finish second if they win at Olympiakos or if Sporting do not beat Barca. Defensively they were bad first time round against Mourinho's men and, having scored seven in their last two games, United look good to win this by more than a goal. Their hopes won't be helped by the fact that Antonio Conte's Blues still have plenty to play for too, as they need a win to guarantee top spot ahead of Roma.
Celtic face a crunch clash against Anderlecht knowing if they avoid defeat by three goals they will qualify for the Europa League. Napoli, who lost their unbeaten start to the Italian season with a 1-0 defeat by Juventus on Friday, are looking to reach the last 16 for only the third time. Liverpool need at least a point to be assured of qualifying and winning the group.
Also, Barcelona superstar Lionel Messi and Real Madrid legend Raul both did it when they were aged 21.
A day later, Liverpool can secure top spot in Group E by beating Spartak. Mourinho's men ran out 4-1 winners in Moscow earlier in the season when Romelu Lukaku scored twice in a game United dominated.
The draw looks a big runner at 12/5 when Manchester City head to Shakhtar Donetsk this week. If Porto finish level on points with Leipzig, the Portuguese side will qualify due to their better head-to-head record. Basel will also qualify if both sides lose or draw their matches as they have a superior head-to-head record against the Russians.
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