You should be able to verify your alias_maps setting with:
Code:
# postconf alias_maps
That will return something along the lines of
Code:
# alias_maps = hash:/etc/aliases
Make sure that's the file that your aliases are configured in. Then run:
Code:
# newaliases
# postfix reload
That should do it for you.
If the above doesn't work, you might try aliasing root to a local user:
Works for me on FreeBSD 8.0-RELEASE