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Pape Sarr scored in a 2-0 win for Tottenham Hotspur.
England captain Kane, who joined for a league record 100 million euros last week to solve Bayern's scoring problems, slotted their second goal in the 74th minute after setting up Leroy Sane for a fourth-minute opener.
Axel Disasi cancelled out Luis Diaz's opener for Liverpool.
Despite a stellar scoring record he failed to win any domestic or international titles with Spurs.
Bayern did not disclose the transfer fee, which media reports have put at around 100 million euros ($109 million). That would be a Bundesliga record.
Should it be completed, Kane's move would be the most expensive transfer in Bundesliga history with an expected fee of about 100 million euros.
The 24-year-old French captain, who still has one year remaining on his contract, is unwilling to renew his contract with PSG.
He becomes the first Australian to manage a team in the Premier League and will join Spurs on July 1.
Argentine Pochettino, 51, will take over from interim boss Frank Lampard on July 1.
Everton will extend their unbroken 69-year stay in the English top flight as midfielder Abdoulaye Doucoure's stunning strike earned them a 1-0 victory on the final day of the season.