Four-times champion Roger Federer was knocked out of the Masters Cup in Shanghai on Friday after a three-set defeat against Andy Murray.
Murray's 4-6, 7-6, 7-5 win in the last Red Group match meant the Swiss world number two failed to progress to the semi-finals for the first time in seven consecutive appearances.
The 27-year-old Swiss, who was chasing a record-equalling fifth title, needed to win his final round-robin match to progress to the knockout stage but succumbed to the Scot's eighth match point after an enthralling three-hour contest.
In-form world number four Murray had already qualified for the last four and will meet Russian Nikolay Davydenko on Saturday for a place in the final.
Earlier, world number nine Gilles Simon dismissed Radek Stepanek 6-1, 6-4 to win his final group encounte and Federer's defeat meant he progressed to the last four.
The 23-year-old, who won his ticket to the season finale when world number one Rafael Nadal withdrew injured, finished with a 2-1 record in the round robin and became the first Frenchman in the knockout stage since Sebastien Grosjean in 2001.
Czech world number 27 Stepanek came in at the last moment as a replacement for injured American Andy Roddick on Wednesday and, with nothing to play for, struggled to contain the dynamic young Frenchman.
Simon claimed the first set when the Czech netted after just 25 minutes and encountered only marginally more resistance in the second.
For me it was just an honour to be here, it was a great experience and a great motivation for next year," said Stepanek, who will be 30 later this month.
"Gilles played a great match ... I tried to play my best tennis here this week."