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Also, Tomas Berdych defeated Kevin Anderson of South Africa 7-6 (5), 7-5, to make the final eight, while Pablo Andujar also advanced after fellow Spaniard Daniel Gimeno-Traver retired.
Second-seeded Roger Federer and third-seeded Andy Murray also have third-round matches later Thursday.
Williams dispatched Maria Kirilenko of Russia 6-3, 6-1, after Sharapova put away Sabine Lisicki of Germany 6-2, 7-5.
Williams dominated Kirilenko, who dropped the first set with one of several unforced errors. The defending champion also used a strong serve and return game, working the 12th-ranked Russian back and forth on the baseline of the red clay court with her precise forehand drives.
"I just felt really relaxed, like I was taking my time," Williams said. "I had been missing my serve when I was hitting it harder, so I took some pace off and didn’t hit as hard as I usually do.
"It was easy because when you take off pace you don’t hit as hard and don’t exhaust as much energy. And hitting a serve or a winner are both fun."
Williams will face Anabel Medina Garrigues of Spain, who reached the quarterfinals after Yaroslava Shvedova withdrew with a right arm injury.
The 15-time Grand Slam winner called Medina Garrigues a "grinder" and predicted a "tough match" in front of the Spanish crowd.
Williams beat Sharapova in the quarterfinals last year en route to the title. This year they are on opposite sides of the bracket, meaning they could only meet in the final.
Sharapova used her big serve to take the first set with relative ease, but Lisicki put up resistance in the second.
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