We are also experiencing this same issue in our Exchange 2016 CU21 environment. We have two servers in a DAG. If a users mailbox is is hosted on server A then Busy/Free information does not populate in scheduling assistant for any user who's mailbox is hosted on server B and vice versa. If they are hosted on the same server scheduling assistant works correctly.
The virtual directory is populated correctly in Exchange admin center for both servers. I can also browse to the virtual directory in Edge from the client machines with no problems. The SSL is valid. Authentication is set up for Anonymous and Windows for EWS in Exchange Back End on both servers.
One thing I find odd is that the error logged in Event Viewer logs the virtual directory URL using the machine name NOT what is set in Exchange Admin Center.
Possibly and issue with InternalNLBBypassUrl? I have tried setting it to various URLs to no avail.
Any help would be appreciated! I am out of ideas.