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Tottenham Hotspur surrendered an early 2-0 lead at Wolverhampton Wanderers but eventually won 3-2 on penalties as manager Nuno Espirito Santo claimed his second win of the season against his former club.
Chelsea manager Thomas Tuchel made 10 changes to his starting lineup and German striker Timo Werner took his opportunity to give his side the lead in the 54th minute as he headed a Reece James cross past Villa keeper Jed Steer.
It was Werner's first goal of the season and he wasted another chance to make it 2-0 before Villa hit back through youngster Cameron Archer's header to send the tie into the penalty shootout.
Ben Chilwell struck the bar when he could have won it for Chelsea but James made no mistake as his spot kick found the top corner of the net.
Brighton and Hove Albion's impressive start to the season continued as they cruised past Swansea City 2-0