Nicolas Roche slipped down to fifth overall after a gritty ride in the fifth stage of La Vuelta a Espana on Wednesday.
The Team Sunweb man is now 57 seconds behind new red jersey holder Miguel Angel Lopez, who relished the steep climb into Alto de Javalambre, taking fourth in the stage for Astana Pro Team.
Spain's Angel Madrazo claimed an improbable breakaway stage victory.
Sam Bennett (Bora-Hansgrohe) crossed in 167th but he's still top of the points classification.
The 171km stage, which contained three categorised climbs, started in L'Eliana on the coast before finishing at the Javalambre Observatory nestled in the mountains of the inland Teruel province.
In the first of nine summit finishes in this year’s race, Madrazo, of Burgos-BH, was involved in a three-man breakaway alongside team mate Jetse Bol and Jose Herrada of Cofidis.
The Spaniard appeared in difficulty as the race progressed, losing the other two on numerous occasions, only to drag himself back into contention before the start of the final climb of the day, the 11km Alto de Javalambre which peaks at 1,950 metres.
He was then dropped with four kilometres of the climb to go, yet improbably caught up with just over a kilometre remaining.
Madrazo, wearing the king of the mountains jersey, then made his move 200 metres from the end to claim a memorable stage victory, with Bol making it a one-two for Burgos.
Lopez, who was wearing the white jersey for the leading young rider, raced away from a small group of overall contenders in the final kilometres to power into red.
Primos Roglic moved into second place overall, 14 seconds adrift, while Nairo Quintana is third, 23 seconds back.
Roche, who had led the race for the past two days, finished the stage in 14th, two minutes 17 seconds behind the stage winner.
The riders will remain in the mountains on Thursday for a 199km stage, departing Roba de Murielos before finishing atop the Puerto de Ares climb.