Victoria Azarenka, Marin Cilic, Radek Stepanek, Steve Darcis and John Isner have seen their Wimbledon hopes ended by injury.
Azarenka, the second seed, slipped uncomfortably during her opening match against Maria Joao Koehler, but recovered sufficiently to finish the match.
However, the Belarusian, scheduled to open against Flavia Pennetta on Centre Court, confirmed her withdrawal through injury moments before she was due to play on Wednesday.
Marin Cilic pulled out of his second-round tie against Kenny De Schepper with a left knee injury. The 10th seed was tipped for a strong run, having reached the final of Queen’s, and eased to an opening victory.
Cilic could also have been Murray’s potential quarter-final opponent, and was on track to meet Jo-Wilfried Tsonga in the last 16.
Stepanek was trailing Jerzy Janowicz 6-2 5-3 when an upper left thigh injury put paid to his tournament.
Darcis, the conqueror of Rafael Nadal in the first round, cited a shoulder injury for his withdrawal.
The Belgian, ranked 135 in the world, stunned Spain’s twice former champion Nadal in the first round on Monday and had been due to take on Poland’s Lukasz Kubot in the second round.
Precious little was known about the 29-year-old from Liege until he turned tennis logic on its head by defeating the twice former champion in straight sets.
There was no partying though as it was straight back down to business for the son of a tennis coach who sports a shark tattoo on his arm and supports Anderlecht.
But now Darcis follows Lukas Rosol who also stunned Nadal last year but lost his next match – albeit due to injury.
Meanwhile, Wimbledon marathon man John Isner was forced to retire after two games of his second round match against Frenchman Adrian Mannarino with a knee injury.
American Isner, who wrote his name into Wimbledon folklore when he played in the longest match in professional tennis in 2010 against Nicolas Mahut, pulled up while serving at 1-1 in the first set.
The 18th seed received extensive treatment on Court Three and attempted to battle through the pain barrier, but had to throw in the towel.
Isner is famous for his part in a record 11-hour-five-minute first round match at Wimbledon against Frenchman Mahut which he won 70-68 in the fifth set.