I spent some time doing a mingw port of GCC4 lately and here's my experimental mingw-special-reactos port for win32:
http://www.reactsoft.com/mingw-special-reactos-20050510.zip
The reactos tree fully compiles from rev. 15198 on and appears to work fine. However, please read notes.txt inside the archive to get it to work properly (default paths are messed up, so you have to set up three environment variables).
Compiling reactos with it will produce quite a bunch of warnings, mostly from 3rd party libraries (e.g. oskittcp, mesa32), the imported wine code and explorer.
Best Regards,
Thomas