@cchrisman
Without testing to make sure, to enroll the user with SIS ID of jdoe525, you should use:
enrollment[user_id]=sis_user_id:jdoe525
When I first started using Canvas, there were some places where SIS IDs were not accepted so I cached the Canvas IDs locally and just refer to those. Since then, things have improved. I noticed that most places I encountered this is where it said id rather than user_id. The name of the property here is user_id, so it should work with the sis_user_id.
If you have tried the above and it doesn't work, then make sure that you can create an enrollment using a Canvas user ID. That will make sure that the rest of the form data is correct and that the real issue is just the SIS ID part and not something else with the request.