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I think that you have to be very careful - I am thinking about the genuine copy validation / activation that XP and Vista have. If you ever manage to boot a VM from a partition that usually boots as main OS (you might manage to do this using Xen) Windows might see too many changes at once in the hardware (e.g. changing from real graphics card & network drivers to the virtual ones delivered by vmware, RAM size depending on how much you allocate for the VM, etc...) and might require a new online activation which might result in an invalidation of your key and the need to buy a new original copy. This happened to me when running the OS non-virtualized I changed at once graphics card and RAID card at once - I finally had to call the Microsoft support and ask them if they could pleeeeease give me a new activation code which I could use only once.
If I would be you I would first create an image file, so a copy, of the OS using dd and then boot it using Xen and see what happens - if everything works fine you could try booting the "real" OS. But again this could not work because e.g. if you have AHCI for the HD controllers switched on and Windows is configured with such AHCI drivers, it might crash when it suddently has to boot with normal non-AHCI drivers. Mmmhh..., I would personally continue to install the OS from scratch, or just copying a "master" installation using the VMware tools (don't have any experience with VirtualBox).
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