A male who hasn't seen any James Bond movies? That's got to be pretty rare in the US.
oh I know and he hasn't even watched Star Trek besides the Abrams movie
or Stargate Sg-1
Then put aside Bond, a great movie series, yes, but getting him into Star Trek is five times more important.
But if you want good films from each actor, show him these:
Dalton: The Living Daylights
Brosnan: The World is Not Enough
Those are my top four favorites. Picking one from Lazenby is easy, and Craig's two were filmed in order. Personally, I's wait till last to show your boyfriend those.