A Brooklyn Nets team featuring James Harden, Kevin Durant and Kyrie Irving playing together for the first time lost 147-135 to the Cleveland Cavaliers after second overtime.
'The Big Three', among the current highest paid NBA stars, played more than 48 minutes and combined for 28 points in the fourth quarter.
But Collin Sexton scored a career-high 42 points to win it for the Cavaliers.
He also scored a three-pointer with 1.2 seconds left in the first overtime.
Durant led the Nets' scoring with 38 points, but missed a potential game-winning shot at the buzzer in the first overtime as the Nets lost a five-point lead with just under two minutes remaining and saw a four-game winning streak ended.
The Nets are fifth in the Eastern Conference with nine wins and seven defeats and the Cavaliers are one place below them.
Centre Joel Embiid scored 42 points and managed 10 rebounds as Eastern Conference leaders the Philadelphia 76ers overcame the Boston Celtics 117-109. Tobias Harris added 22 points for the Sixers, who have won eight of nine at home.
The Los Angeles Clippers took advantage of city rivals the Lakers' slip-up on Tuesday with a 115-96 victory over the Sacramento Kings to go top of the Western Conference.
Kawhi Leonard produced a man-of-the-match performance with 32 points, six steals and five assists as the Clippers recorded their fifth consecutive win.