AFAIK, there is no way to do this that would be the same as switching to PAL from the boot menu.
However, there are some tricks you can do such as running a program to switch to PAL when booting workbench. If you dig around old threads here, there's a few cases where some people have soldered some bit on the cd32 motherboard and got it to boot up as PAL, although I believe there were a few problems and it was not necessarily truly in PAL mode.
However, if you are running WHDLoad games in workbench, you can set it to run in PAL, and that should be good enough.
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