The elite 36-hole event is for the winners of the year's four majors. British Open champion Phil Mickelson chose not to play and was replaced by defending champion Padraig Harrington.
PGA Championship winner Dufner bogeyed the 14th and 16th holes as the breeze freshened en route to a two-under 69, while Masters champion Adam Scott, who had a bogey and double-bogey on the same two holes, was a further shot back.
Harrington mixed three birdies with four bogeys and a double-bogey for a three-over 74.
Rose made an ideal start at the par-four first, where he hit a poor drive but then nailed his approach shot from 186 yards for a tap-in birdie.
"My tee shot, I thought it was going to go straight in a bush, but it landed in the cart path just in front of that bush and hopped over, so I caught a good break there," Rose told reporters.
"I didn't really play my best today but I kept the ball out of some really bad spots. I felt like I putted really well (and) read the greens well."
The final round will be played on Wednesday.
(Reporting by Andrew Both in Cary, North Carolina; Editing by Frank Pingue)
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