Excellent topic, thanks for starting it. As much bad press as Bond gets (sometimes deservedly), it is also nice to note when they do something right.
My pick for favorite underrated scent is West Broadway.
Has a similar sweet/candy vibe ala Cannabis Santal and A*Men, but still holds its own in distinction and with a definite hint of class in there that makes it more wearable. Also has excellent longevity. I'm down to my last 15mls in my 100ml bottle... don't know if I'll buy another (unless I get a really good deal), but I DEFINITELY don't feel my money was wasted on it.