Assuming native mode here...
The main thing you are migrating when doing the upgrade to SQL Server 2014 is the reports, subscriptions, and then your data connections. I can't think of a reason why you would need to put this database in replication just for an upgrade. Also, while it probably could be done (and work) it is not a supported method of upgrade from Microsoft to put the SSRS databases in mirroring configuration. So proceed at your own risk.
Unless you are adding/modifying reports or subscriptions often I would not see why you could not just do a quick migration according to documentation. Perform your testing of the new version with your reports, and then at cut-over time just do a backup/restore one last time.