OK. I can see your problem.
Well, at least users are forced to fix the faulty address immediately. By getting a bounce later most users won't 😉
I know this is not the answer you were looking for so here you go (although I actually think user education never hurts and have not implemented this on my high traffic servers ;-):
Are your users being forced to use SMTP authentication to send? If not make sure you have this in place as the first step. This is important so that your security is not compromised.
Now look at your /etc/postfix/main.cf and towards the end look for
smtpd
recipientrestrictions = .......
You'll see something along these lines:
smtpd
recipientrestrictions = permit
saslauthenticated, reject
unauthdestination, permit_mynetworks, reject
rblclient sbl-xbl.spamhaus.org, reject
rblclient relays.ordb.org, permit
See if it includes reject
unauthdestination and/or reject
unverifiedrecipient and remove those.
This should do the trick (not knowing your configuration there is always a chance something doesn't work as expected).
The drawback is that this is now true for all senders and thus mail will get accepted first and bounced later if for unknown users.
You can "finetune" this so that it applies only to your local users, but this requires quite a bit of fiddling around with your configuration and will "break" Server Admin. If you don't mind, see the following page for more info or ask again 😉
http://www.postfix.org/postconf.5.html
Alex