Despite reaching the final of the Australian Open and the semi-finals of Wimbledon, Djokovic has not reached the quarter-final in any of this year’s Masters 1000 events.
He won the last of his 24 Grand Slam titles at the US Open in 2023.
Qualifying for Turin would have given him a chance to win a record-extending eighth title at the season-ending championships.
Instead, only Americans Taylor Fritz and Tommy Paul remain in contention to take the final two places currently held by Frances Tiafoe and Rafael Jodar.
Djokovic had not failed to qualify when fit since 2017.
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Explore OfferTiafoe’s chances were taken out of his hands earlier on Wednesday when he fell to a 6-3 1-6 7-6 (11-9) defeat by Frenchman Quentin Halys.
Australian Alex de Minaur then failed to take advantage as he lost 7-6 (7-2) 6-3 to Argentine Tomas Martin Etcheverry. A run in Paris could have secured De Minaur’s qualification.
Elsewhere, world number one Alexander Zverev and fourth seed Daniil Medvedev, both of whom have already qualified for Turin, were also beaten.
Zverev said he was “annoyed” by the response to him becoming world number one after a straight-sets loss to Lorenzo Musetti while Medvedev was beaten 6-4 6-4 by Peruvian world number 33 Ignacio Buse.
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