Hi @rddx58 • Thank you for reaching out.
Adding bluecorp.com as custom domain will not automatically update the UPN from bob@bluecorp.onmicrosoft.com to bob@bluecorp.com. You will still be able to sign into O365 Admin center by using bob@bluecorp.onmicrosoft.com.
To update the UPN to bob@bluecorp.com after adding the custom domain, you will need to run below cmdlet:
Set-MsolUserPrincipalName -UserPrincipalName " bob@bluecorp.onmicrosoft.com" -NewUserPrincipalName "bob@bluecorp.com"
To add bob@bluecorp.com as secondary email address, you can use below cmdlet:
Set-Mailbox -Identity "bob" -EmailAddresses @{add="bob@bluecorp.com"}
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