Maybe a night shoot with enough moon to provide cloud lighting but not so much to necessitate a heavy ND filter? Maybe have the subject sitting to block the background (shaded to stop the ambient light lighting them!) before flashing them?
http://www.shariblog.com/2013/06/long-exposure-shots-under-the-night-sky/
(found following the Monster camera link in IanDJ's thread)
In terms of lighting, it would work, yes... but there's no way the model will sit perfectly still for the length of the ambient exposure, so when you flash the model in there will be a soft black halo around the edges where he or she has moved. It's retouchable of course... but requires just as much work as compositing. The results will be the same too, so go with the easiest method.
Been there... done that.
I tried this with my Going Home series I did a few months ago. Like Phil, I wanted to avoid compositing... but it was just too problematic, and would have required just as much retouching to remove the dark vestiges of ambient exposure anyway. Also... some of my locations didn't lend themselves to models in dresses
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If there are soft billowing fabrics involved, that will just cause mayhem too. The models in that link above are sitting.. or leaning, this of course makes it MUCH easier to remain still. Would a sitting model work in your idea Phil? If so, while tricky, and requires discipline in your models... it may be an answer. They'll almost certainly require retouching though.
It also depends if you want the results to look flash lit or not. If you want the model to appear to be naturally there, and naturally lit, then that becomes so problematic on location that it would definitely be easier to comp.
If the model was there in the shot below, and flash lit, A) the flash would actually be in shot, and need retouching out, and B) would not look as natural as recreating the lighting in the studio. In short, would it actually look as natural if she was flashed on location? I think not.
If you don't mind the models obviously being flash lit like the link Nod posted, then I'd say get them to lean or sit, remain still, and then flash at the last minute. If you want natural looking lighting... shoot in the studio and comp. It's all about the image at the end of the day. Shooting for comp is as much of a skill as solving it as one exposure, as you still have to be very good with lighting to achieve either convincingly.