Transport rules can be used to mimic the behavior as well, and would have to be tested to each customers' desired configuration.
If you people prefer to reject messages for non-existent user, Create a Distribution Group and add all users as a members.
1. DL Contains all members.
2. If the sender is Located "Outside the Organization"
3. Block the Message.. " Reject with Explanation"
4. Except if the Recipient is member of . Distribution Group (Contains all users as members)
DomainType needs to set it as InternalRelay, Do not try this in co-existence scenario.
Changing the action to Redirect to other mailbox, Will make the above Transport rules to work in Catch all mailbox concept.
Regards,
Kingson