Astarion- free spirit guy, so probably most open for endings now. "Good" he becomes a Vampire Hunter? (Vampire Vampire-Hunter) "Evil" something like killing his master, taking his role and enslaving as many people as possible.
That why I think leaving Alignment is good idea as just opens more possibilities. Also there is lower risk of non sense like some characters in Pathfinder: Kingmaker have been.
But notice that used the alignment system to make your point.

The alignment is the goal post, it's the umpire's decision, it's the game telling you if you completed the quest or not. It structures the world we play in.
I do agree that Astarian is the least likely to transform but I'm still hoping that he will be the Spike to my Buffy. I mean if you just look at Spike in the first few seasons there's not much chance he'll change, right?