IMO this is pretty viable. Digital and slides have in common their limited highlight latitude, IMO the DSLR may provide a very acceptable preview on the resulting slide. Personally I would adjust that procedure with 35mm film. For well selected sample scenes I would use the same base exposure, then I would bracket both the 35mm film and the digital shots. This would tell what exposure compensation to use in the digital camera to take the preview shot in the way highlights would result similarly blown when overexposed. Perhaps to preview the shadows another exposure compensation has be used.
Also it would be important to disable some features in the DSLR.
Im my case, I tried to use the DSLR to preview/learn the color filtration effect, on a doubt (orange vs red) I have placed each filter in the DSLR and shot BW mode. What had been really useful to me was using 35mm to bracket filter type vs exposure just to learn, but sometimes y used the DSLR for the filter effect preview before spending a big sheet.
Still, for slides, what resulted the most useful to me was bracketing+spotmetering+taking_notes in different situation, to know how sky/clouds/terrain/people results at different over/under exposure levels, so know I've a criterion to refine and balance the exposure, and to select a graded ND. Negative film is more forgiving if enough exposure is provided... But you know, slides have to be nailed... and is the slide is a sheet then better to check it twice !!! "Mesure twice and cut once" = "Meter twice and nail the exposure of the slide"