The hosts eventually restored parity in the 73rd minute after Robert Lewandowski headed home Thomas Muller's chip into the box to make it 1-1 on the scoreboards.
It was however short-lived joy for the "Bavarians" as Adamyan wasn't done with the scoring and wrapped up his brace after nutmegging Boateng and overcoming Neuer for the second time in the 79th minute.
Bayern increased the pressure but their efforts in the closing period couldn't prevent the first defeat of the season.
With the defeat, Bayern remain on the front spot for the moment meanwhile Hoffenheim climbed to the 11th place of the standings.
Elsewhere, Borussia Dortmund grabbed the lead twice but in-from Freiburg reaped a late draw on an own goal from Manuel Akanji to move to the 2nd place of the table.
Leipzig and Bayer Leverkusen missed the chance to go atop the standings after sharing the spoils following a 1-1 and Mainz ended their two-game losing streak after beating newly promoted Paderborn 2-1.
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