Should I risk being fired to help the students?
If you are fired you won't be able to help anyone.
But instead of being proactive in speaking with them, you can just be vigilant and deal with problems as they occur. If you maintain open communications with those who might be on the receiving end, you will probably hear about issues. If necessary you can take them to the supervisor.
But disobeying a supervisor for a new employee isn't likely to be especially helpful.