I presume they have rusted under the surface and seized into the substrate. What do they screw into? Are they coach screws?
If you have a blowtorch with a fine pencil flame, you can heat the head, and it will probably crumble the rust or scorch the wood enough to unscrew. If plasplugs, they will melt. Protect the timber with a piece of metal or tile with a hole just big enough for the head.
But I had some galvanised studding into RC fenceposts rusted so badly that I had to drill them out. I drilled the heads off and used a fine drill beside the studs.
I use stainless bolts now, and big stainless washers.