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Visitors Chelsea desperately needed a response after back-to-back humiliating away losses, with last Sunday's 6-0 thrashing by Manchester City following a 4-0 reverse at Bournemouth.
After champions Manchester City's shock loss at Newcastle United on Tuesday and Manchester United's home draw with Burnley, Liverpool caught the bug at home to Leicester City.
Kane's 26th-minute spot kick was awarded after a lengthy, but correct, VAR decision and means Tottenham remain on course to claim their first silverware since winning the League Cup against Chelsea in 2008.
Manchester United were 11 points off the fourth Champions League spot when Solskjaer took over a fortnight ago but their gap behind Chelsea is now already down to six points.
The Premier League club paid 64 million euros for the 20-year-old, Dortmund said in a statement.
Chelsea kept up their pursuit of the Premier League's top three clubs with a 1-0 win away to London rivals Crystal Palace on Sunday.
Liverpool also fell behind but stormed back to beat Burnley 3-1 and cut the gap on leaders Manchester City to two points.
Arsenal and Chelsea were among seven teams to reach the Europa League knockout stage, while last year's runners-up Olympique de Marseille were eliminated at the group phase.
The London club are two points behind leaders Liverpool and one point ahead of champions Manchester City.
Two goals from Anthony Martial had appeared to have earned Mourinho's Manchester United a much-needed comeback win after they went 1-0 down in the first half.