If you're familiar with scripting:
You can write a client script that validates each line.
If the line being added WASNT a discount, it would allow the line to be added.
If the line being added WAS a discount;
The script would loop through all the other lines, checking for the specific item.
If that specific item was on the order, a pop up could be thrown that says "Cannot Add Discount if [specific item] is on the order" and it would prevent the discount line from being added.