Craig Conway (front) gets away from Dunfermline's Gary Mason
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New Dunfermline manager Stephen Kenny watched from the stands as the Pars secured a much-needed win.
Barry Robson headed the visitors in front in 51 minutes after he converted Craig Conway's cross.
Greg Shields equalised for the Pars in 76 minutes when he drilled the ball home from six yards after a Scott Morrison corner.
The Pars clinched victory when Gary Mason converted Stevie Crawford's cross with two minutes remaining.
Assistant boss Craig Robertson took charge of the SPL bottom club for the final time and was boosted by the return of goalkeeper Dorus De Vries, defender Scott Wilson and midfielder Darren Young.
United boss Craig Levein named the same side which defeated Kilmarnock last weekend.
A poor first half with few chances sprang into life four minutes from the break with referee Alan Freeland coming under fire.
First, he waved play on despite Lee Mair being only three yards away when he blocked a Crawford free-kick.
When the ball did break, Robson raced through and held off Scott Wilson on the by-line before appearing to be hauled down, but Freeland waved aside the visitors' claims.
Simmons saw an acrobatic effort fly past near the break before Freeland was booed off.
Stephen Kenny applauded the Pars fans before kick-off
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Levein's men quickly regained their grip on proceedings and Hunt should have scored from Conway's clipped cross on 51 minutes but again nodded wide with De Vries struggling.
But United's goal was only delayed another 60 seconds after De Vries was badly caught out.
Conway swung over another cross from the left and, as De Vries rushed from his goal, Robson headed past him into an empty net from 15 yards in the 52nd minute. Conway then chipped narrowly wide before Crawford quickly tested Stillie from 18 yards.
The Pars had crept back into proceedings and claimed an unlikely leveller in the 76th minute.
Substitute Scott Muirhead swung in a corner and Hamilton nodded the ball back for Shields to drive the ball home from just inside the six-yard box.
Incredibly, the winner duly arrived with two minutes remaining to send East End Park into raptures.
Crawford broke free on the right and his cross was flicked on by another sub, Freddy Daquin, to allow Mason to send the ball past Stillie.
Dunfermline: De Vries, Shields, Wilson, Scott Morrison, Labonte, Young, Mason, Simmons (Daquin 60), Owen Morrison (Muirhead 60), Hamilton (Ross 81), Crawford. Subs Not Used: Paterson, Woods, Bamba, John Dunn.
Booked: Shields.
Goals: Shields 76, Mason 89.
Dundee Utd: Stillie, Kalvenes, McCracken, Kenneth, Mair, Duff, Kerr (Cameron 90), Conway (Goodwillie 79), Robson, Hunt (Samuel 65), Robertson. Subs Not Used: McLean, Archibald, Proctor, Smith.
Goals: Robson 52.
Att: 6,129
Ref: A Freeland