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Petra Kvitova overcame a sluggish start and 10 double faults to beat Madison Keys 6-7(6), 6-4, 6-3 and advance to the women's singles final, where she will face Caroline Garcia, the first qualifier to reach the final of a WTA 1000 tournament.
In the men's section, world No. 1 Daniil Medvedev and fourth seed Stefanos Tsitsipas defused big-serving American threats Taylor Fritz and John Isner to reach the semifinals.
Taylor Fritz blasted his way to a 6-3, 6-2 win over Australian Nick Kyrgios while Cameron Norrie fought back to beat former world No. 1 Andy Murray 3-6, 6,-3 6-4 in an all-British clash.
He will next face unseeded Chilean Cristian Garin, who beat Kyrgios's compatriot Alex De Minaur to enter the last eight.
The fourth seed, Tsitsipas, won 6-2 6-3 7-5 on Court One on Thursday.
Men's top seed and defending champion Novak Djokovic, chasing a 21st Grand Slam title after a troubled year, will open his campaign against South Korea's Kwon Soon-woo.
The German defeated his Spanish opponent, 6-4 6-4 4-6 7-6(7).
The Dane succeeded in getting Tsitsipas out of his comfort zone on the baseline, sending his tall opponent to the net with drop points and stretching him wide off the court with deep cross-court balls.
Djokovic defeated Tsitsipas 6-0, 7-6 for his first title of 2022.
Alcaraz became the first player to beat Rafael Nadal and Djokovic at the same clay court event.