It looked like both teams would settle for a share of the spoils but Dortmund had the last laugh, as Alcacer lifted a free kick over the wall into the top-right angle to give Dortmund a late 4-3 victory in the dying seconds of the game.
With the result, Dortmund stay atop the standings whereas Augsburg slipped from the 8th to the 9th position.
Elsewhere, Bobby Wood's first-half brace smoothed the way for Hannover's 3-1 victory over struggling Stuttgart.
Schalke reaped their second victory in the league after easing 2-0 past Dusseldorf on the second-half goals from Weston McKennie and Gudio Burgstaller and Hertha Berlins shared the points with Mainz following a goalless draw.
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