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Two goals from Gary Medel and an Ivan Rakitic strike was enough for the home side to prevail with Riki scoring a consolation for Deportivo.
CNN: Bayern on cruise control as Arsenal awaits
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Chile, shorn of suspended trio Marco Estrada, Waldo Ponce and Gary Medel, were always up against it after conceding twice in four minutes shortly after the half-hour mark.
BBC: Brazil 3-0 Chile
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In a rare struggle to monopolise the ball, Spain looked riled - but while Chile worked overtime to establish the upper hand they lost their discipline - both Gary Medel and Waldo Ponce were rightly booked for nasty tackles and will miss the match against Brazil.
BBC: Chile 1-2 Spain