There's discussions on these forums.
A rule of thumb could be that if you are managing "content" you use a system like Alfresco. If its a highly relational app that then use a RDBMS.
Some examples. If its a "newspaper publishing" type app, approving and publishing "articles". Or a document library. That's suited to a system like Alfresco.
If its your accounting system with lots of complex tax rules etc then that needs to be in the RDBMS.
But it then becomes blurred. Say that the accounting system contains lots of scanned invoices that need to be transformed, approved and archived. Then you could end up using both Alfresco AND an RDBMS together. Practically this will just mean putting appropriate keys into each application. And thinking through the rules for deleting data.
The WCM world is similar If you are presenting a web interface to a relational database then Alfresco may not suit. Equally if your web site consists of bits of content, some images, some text, some code, some PDFs to download, that's where alfresco comes in.