Once you have migrated your content over to the new site, then create a PHP algorithm that will figure out the new link that you intend to use, and redirect using a 301 header (Moved Permanently). It's possible to even change the PHP extension to be handled as an ASP.NET page by your server, so you could code the algorithm in .NET if you choose to do that once you have finished the redevelopment of course.
This will tell search engines that the content has moved to the ASP.NET pages, which should help in your page rankings as long as people still link to either page, and it will also keep people from getting 404 Page Not Found errors when you have migrated the system.