Chara won a flip and went first Thursday, choosing the Red Wings' center, who is third in the league in assists with 39 and tied for third in points with 53.
Alfredsson's first choice was Ottawa defenseman Erik Karlsson.
Alfredsson chose Ottawa forward Jason Spezza, Los Angeles goaltender Jonathan Quick, Philadelphia forward Claude Giroux and Pittsburgh defenseman Kris Letang with the remainder of his opening five choices.
Steven Stamkos of Tampa Bay, the NHL's leading goal scorer this season with 32, wound up on Alfredsson's team.
Sunday's face off in Ottawa will be 4 p.m. EST.
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