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I have just installed the Office 2016 Preview and am severely disappointed to find that I cannot send from the alias within the new client.
It's a work in progress in conjunction with the move of Outlook.com to the Exchange Online platform. Once that is completed and your account has been migrated, sending from an alias address will be possible without any additional configuration in Outlook 2010 or later.
Until then, you can configure the alias as an additional POP3 account and configure it for sending only.
This is still not solved. I am really thinking to move towards the G* option. Can at least someone explain the rationale behind this? Both domains belong to me and I cannot send "from" my alternate domain address?