@Marc Fritz , UPN (UserPrincipalName) and Domain/Username are not the same. In the domain/username format, the value in the username section comes from the attributeValue of SamAccountName that is available with On-Prem user objects.
Ideally with default AD Connect Sync rules, this attribute "SamAccountName" gets synced to Azure AD as "onPremisesSamAccountName". Inoder to find the onPremisesSamAccountName attribute value from cloud, you would have to use the GraphAPI calls, since this attribute is only exposed to Graph API.
You can use the following GraphAPI call https://graph.microsoft.com/beta/users?$select=userPrincipalName,onPremisesSamAccountName
Also, you can refer to the following documentation to get an understanding regarding Graph API and how to use it: https://learn.microsoft.com/en-us/graph/use-the-api
For using the Postman tool to make Microsoft Graph API calls: https://learn.microsoft.com/en-us/graph/use-postman
Hope this helps.
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