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ALPE D’HUEZ, France — The 100th Tour de France had been billed as a battle between a rising star and a fading one: Christopher Froome versus Alberto Contador, the commanding leader of this year’s Tour against a once-dominant Grand Tour racer who has struggled all year.

Stage 18 seemed custom-made for their rivalry. For the first time in Tour history, the riders would ascend the daunting Alpe d’Huez twice, with a treacherous descent from the Col de Sarenne in between. As if to fuel the prestage drama, Froome had almost crashed into Contador during a furious downhill chase on Stage 16, and later chided the Spanish rider to ride more safely.

As if on cue Thursday, Contador sped away from Froome during the descent from Col de Sarenne, all but daring Froome and his teammates on Sky Procycling to follow their daring lead. It took awhile, but they eventually did, catching Contador and then leaving him behind as the race turned up Alpe d’Huez for the second time.

At the finish, Froome extended his lead over Contador to 5 minutes, 11 seconds. Nairo Quintana, a Colombian climbing sensation on the Movistar team, gained more than a minute on Froome and moved into third place.

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The stage was won by Christophe Riblon, a French rider on Ag2r-La Mondiale, who caught the weary American Tejay van Garderen of BMC less than a mile and a quarter from the finish. Van Garderen, a Tacoma native who has seen his fortunes improve after a miserable initial two weeks on the Tour, finished the stage in second.

Although he solidified his lead over Contador, Froome showed a certain vulnerability on the stage. He had crushed his top challengers twice on mountain stages in this Tour. But in the final stages Thursday, he motioned repeatedly to his team car for help, until his durable teammate Richie Porte delivered him some food.

As Froome slowed to eat, Quintana and Joaquim Rodríguez of Katusha distanced him. Froome was given a 20-second penalty for eating outside the designated feed zone.

A reporter later turned the doping-suspicion issue on its head, asking the British rider whether his sugar fit on Alpe d’Huez suggested that he was human after all.

“It’s crazy hearing people talk like this,” Froome replied. “Any athlete can have a sugar low at the end of a race.”

Although Froome’s lead seems commanding, the race is far from over. The 127-mile stage Friday includes two beyond-category climbs, including the 11.8-mile Col de la Madeleine. As they have throughout the race, Contador’s Saxo-Tinkoff team and Quintana’s Movistar teammates, who have proved very strong, are expected to push the speed up aggressively in an attempt to break Froome’s will.

Riblon’s victory came at the end of a long breakaway in which he, van Garderen and Moreno Moser of Cannondale took turns trying to escape from one another.

Van Garderen, who finished fifth last year but was in 50th place at the beginning of Thursday’s stage, pushed into first place during the second ascent of Alpe d’Huez.

At one point he had what appeared an insurmountable half-minute lead over Riblon. But with less than 2 kilometers to go, surrounded by screaming, flag-waving French fans, Riblon stood on his pedals and accelerated past van Garderen, who seemed helpless to respond.