The 21-year-old Russian shocked the former World No. 1 on the WTA Tour, who held this position for 67 weeks 7-6 (7-4) 6-3.
Meanwhile, fourth seed Caroline Wozniacki cruised to the next stage of the tournament with a comfortable 6-0 6-1 win over American Madison Brengle in less than an hour.
In the men's category, Juan Martin Del Potro also lost to Canadian Vasek Pospisil 6-4 7-6 (9-7)
The Argentinian is just returning to the court after suffering a wrist injury that had kept him out since January.
Friday's play features British number ones Andy Murray, who faces American Donald Young, and Heather Watson, who plays Germany's Angelique Kerber.
World number three Rafael Nadal takes on fellow Spaniard Nicolas Almagro, while women's world number one Serena Williams plays Romanian Monica Niculescu. BBC
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