Hmmm, 24 makes me think he's into the more fast paced action-orientated films, but Alias has some very dramatic, slow moving plots (by today's standards anyhow) from what I can remember of the show - never really a fan myself.
So I'd suggest starting him off with some of the more recent films and working backwards.
Casino Royale. Goldeneye. License to Kill. On Her Majesty's Secret Service. Then the all-time classic, Goldfinger.
So I'm not much of Moore fan, but you said five, and there's been six Bonds, so someone wouldn't make the cut, plus I think OHMSS is hugely underated.