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Don't think you can. You can only sync it with what ever is in the folder you've set it to sync with. It would only be a very small copy on the ipod too.
The iPod should appear in Finder IIRC.
You should be able to browse the iPod as if it was an external disk drive, then cut and paste (or drag and drop) them from the Photos folder on the iPod to a location on the Mac's HDD.
I could be wrong though. I haven't touched a Mac for months.