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The boot of full-back Melvyn Jaminet steered Toulouse to a narrow victory that earned them a home draw in the Heineken Champions Cup last 16 and condemned Munster to a road trip in the knock-out stages.
Jaminet, deputising for the suspended Thomas Ramos, kicked 15 points as he took the game away from the Irish visitors in a second half which saw the lead change hands four times before the hosts finally clinched a 20-16 win.
Five-time European champions Toulouse finished second in Pool B behind holders La Rochelle, while Munster missed out of a top-four finish that would have guaranteed a game for them at Thomond Park in the round of 16 at the end of the Six Nations.
Toulouse started the stronger, and stormed into an eight-point lead thanks to the first of Jaminet’s five penalties in the second minute.
Things got even better for the hosts five minutes later when their Argentina wing Juan Cruz Mallia got past Shane Daly to cross in the right corner.
Jaminet pushed his touchline conversion inches wide of the far upright, but he was back on target in the 11th minute to make it 11-0.
Munster needed something to steady the ship and they hit back on the half-hour mark with their first try.
The United Rugby Championship team had made too many unforced errors in the opening quarter, but there was no stopping the outstanding John Hodnett.
Joey Carbery could not add the extras but hit the target with a penalty four minutes before the break to make it 11-6 at the interval.
Both teams came into the game knowing they were safely through to the round of 16, but the real battle was for a top-four finish to guarantee a home draw. That meant they had to go all out to the final whistle.
Having grown into the game, Munster struck with a try from Ireland lock Tadhg Beirne to take the lead in the 50th minute.
Once again Carberry was wide with his routine conversion attempt and two minutes later he was replaced by Ben Healy - not the sort of ending he wanted to a week that saw him dropped from the Irish Six Nations squad.
Jaminet and Healy swapped penalties as the lead kept changing hands, before Toulouse hit the front for the third time in the match with another Jaminet kick after English referee Karl Dickson had penalised Munster for crossing at a line-out in their 22.
There was still only one point in it, but then Healy was sent to the sin-bin for leading with his arm as he carried the ball into a tackle.
That came in the 69th minute and four minutes later the power of the home pack came into play to earn them another penalty which Jaminet kicked to stretch the gap and secure the win.