OH. MY. GOD. Sean Connery <3
My suggestion would be to start off with the originals. Bond "fans" who have only seen the new ones/saw the new ones first and then the old ones just don't appreciate the origins of Bond. They are used to the new style and don't like the old style but CLASSIC BOND >>>>> NEW BOND.
Sean Connery IS Bond so the best ones to watch:
-From Russia, With Love
-Diamonds are Forever
Those are my favourite ones ever. Thunderball is alright as well but not as good as the above mentioned. Just avoid the shitfest that is Never Say Never Again.
Your BF will love Honey Rider. I do, no homo.
FYI, Dr. No is the very first Bond movie.