A domain without users has a complete list of valid addresses, known by Postfix DB, so it can reliably route unknown addresses to the catchall one.
Postfix does not directly connect to LDAP where users are listed. Without a complete list of available mailboxes it doesn’t know if an address corresponds to a user. Hence it cannot route the message to the catchall reliably.
This is the current UI, where the "Accept unknown recipients" switch is disabled for this limitation:

Proposed solution
Discussion
A domain without users has a complete list of valid addresses, known by Postfix DB, so it can reliably route unknown addresses to the catchall one.
Postfix does not directly connect to LDAP where users are listed. Without a complete list of available mailboxes it doesn’t know if an address corresponds to a user. Hence it cannot route the message to the catchall reliably.
This is the current UI, where the "Accept unknown recipients" switch is disabled for this limitation:
Proposed solution
Migrate the "Accept unknown recipients" setting from NS7See Wrong migration of Mail's "Accept Unknown Recipients" setting #7257Discussion