You can use it this way, but it doesn't make much sense:
If you have enough RAM, then the files will be in the filesystem cache (i.e. in RAM) anyway. So, you don't win anything by using tmpfs, but you also don't lose anything.
If you don't have enough RAM, the tmpfs will be flushed out to swap. Now, your Rails sources eat up precious swap space despite the fact there is already a copy on disk in the filesystem. So, you lose swap space and you don't win anything on performance (whether the files are read back in from swap or the filesystem is equally expensive).
If you don't want to take that first time hit until all the files are in the cache, you could put something like this in your development environment startup scripts:
find /usr/lib/ruby/gems/1.9.1/{rails,action,active}* -exec cat '{}' + > /dev/null
Which will read all the Rails files and echo them into /dev/null
and as a side effect pull them into the cache. (Do this while getting your coding coffee.)