"I'm really, really excited about it," said Cain, quoted by MLB.com
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The AL's batting order has Derek Jeter leading off and playing shortstop, followed by Yankees teammate Robinson Cano at second base, Texas left fielder Josh Hamilton, Toronto right fielder Jose Bautista, Detroit first baseman Prince Fielder, Texas third baseman Adrian Beltre, Boston designated Hitter David Ortiz, Texas catcher Mike Napoli and Yankees center fielder Curtis Granderson.
The NL has Colorado's Carlos Gonzalez leading off as the DH, followed by San Francisco center fielder Melky Cabrera, Milwaukee left fielder Ryan Braun, Cincinnati first baseman Joey Votto, St. Louis right fielder Carlos Beltran, Giants catcher Buster Posey, San Francisco third baseman Pedro Sandoval, Atlanta second baseman Dan Uggla and St. Louis shortstop Rafael Furcal.
Braun, who finished fourth in NL outfielder voting, takes the place of the Dodgers' Matt Kemp, on the disabled list because of a strained left hamstring.
Verlander, the reigning AL MVP and Cy Young Award winner, is 9-5 with a 2.58 ERA. He is the first All-Star starter who has won Rookie of the Year, Cy Young and MVP.
Cain, 9-3 with a 2.62 ERA, pitched a perfect game against Houston on June 13. He was picked over the Mets' R.A. Dickey, who is 12-1 but throws a knuckleball that could pose a challenge for Posey.
In 2011 the National League defeated the American League, 5-1. With the victory, the NL now leads the series 42-38-2.