In theory, Sandcastle could be used to document unmanaged code but it would require a tool to produce the equivalent reflection data file that is currently produced by the MRefBuilder.exe tool for managed code assemblies. So far, nobody has done that to my knowledge.
I can't comment on the lack of IntelliSense for unmanged C++ since I don't use it anymore. At a guess, /doc is probably there for the managed code output assuming the same compiler is used but with a few extra command line options.
Using XSL to transform the XML comments to MAML is a possibility but, again, it's an option I'm not aware of anyone pursuing. My guess is that most opt to use Doxygen in this case since it's an established solution.
Eric