Karolina Muchova was a casualty in the first round of the National Bank Open as she was stunned by Oceane Dodin in Montreal on Monday.
The 14th seed was undone by the French qualifier despite Dodin sending down 10 double faults.
The 6-3 1-6 6-2 success was Dodin's first over a top-25 player this season.
Former U.S. Open finalists and 16th seed Madison Keys was also a first-round casualty, going down 6-3 6-3 to Canadian Rebecca Marino.
Toronto-born Marino, currently ranked 220th in the world, won in one hour and six minutes, converting four of her eight break points, while she saved four from five too.
However, there were no such problems for Ons Jabeur, the 13th seed strolling to a 6-1 6-3 victory over Clara Burel.
Eleventh seed Maria Sakkari also had a routine day, her opponent Marie Bouzkova unable to continue with Sakkari ahead 6-4 3-1.
An Olympic gold medallist in the doubles at Tokyo 2020, Katerina Siniakova had more to celebrate in the singles with a 6-1 6-3 win over long-time rival Jelena Ostapenko.
Elsewhere in the draw, Paula Badosa, Sorana Cirstea, Amanda Anisimova, Nadia Podoroska and Fiona Ferro all progressed.
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