In "Communication Breakdown", the latest episode of USA Network's 'Covert Affairs', Annie Walker mentioned to her friend Augie Anderson that "James Bond was a lonely, sad, old man." Her point was that Augie wasn't like Bond; that he wasn't the kind of man who would exploit a woman for intel.
James Bond does exist in Toobworld, and probably under the same situation as established in the first movie version of "Casino Royale" - that the British Secret Service keeps giving that cover name to their top agent so that he will always be a presence in the shadowy world of espionage. That way his legend becomes a weapon against their enemies.
In the TV Universe, James Bond was first seen in the television adaptation of "Casino Royale", but with Barry Nelson as an American spy. He was even called "Jimmy Bond" in the tele-play! But later, after he retired (or was eliminated), other - probably British - secret agents assumed the identity of Bond, James Bond. And we met one of them in his own later years when his path crossed that of U.N.C.L.E. agent Napoleon Solo in "The Return Of The Man From U.N.C.L.E. - The Fifteen Years Later Affair".
The world of James Bond as we know it in the movie universe does exist in Toobworld, but mostly in the form of commercials - blipverts advertising cars, watches, even soda.
As Annie Walker made no mention of the movies or the original novels by Ian Fleming, we can make the assumption that she was referring to Bond as a real person. His exploits probably were part of the curriculum at Quantico, but it's O'Bvious that Annie didn't approve of his methods. He may have even come to one of her classes to give a guest lecture. Afterwards, he probably tried to hit on her, which is how she came by her opinion of the man....