Of course not. They would have broken up, but once the magic show finished she'd have taken him back instantly, saying he wasn't in his right mind, the magic corrupted him, blah blah blah.
He'd have gone back to her because dat ass.
The problem is, with Sunset the villain, her motivations from the very start were different.
She never actually liked Brad like that, he was just a means to an end, an easy way to gain popularity and become the school's IT couple. By the time Brad caught on she was fucking evil, she was already the IT girl and didn't need him anymore anyway.
Brad's motivation in any scenario would only ever be DAT ASS. As the reformed villain he'd get back with her because she'd take him, her being good and all and knowing he was always good inside and loved her deep down et al.
Reformed Sunset won't get back with Brad because she knows those feelings were never real, and she doesn't want to lie to herself or him anymore. Being with him would remind her every day how badly she used him, so it's unlikely she'd be able to stay in the relationship even if they did try getting back together.
Reformed Brad wouldn't think that deeply about it, handwaving it all because they were happy together now.
People think differently. Not just men vs. women, as individuals. Brad and Sunset would have wildly different outcomes with a role reversal because they don't look at things the same way, and who's to say who's way is better?