Hi @Allan Stark ,
go to AD User and Computer, find the user, doubleclick -> attribute editor -> find "proxyAddresses".
add the address
NOTE:
if there are no values at all in the attribute, please add the value like this:
SMPT:primaryEmail@yourdomain.com
smpt:emailyouwanttoadd@yourdomain.com
every further email needs to be added with "smtp:thenyourmail@yourdomain.com"
as Andy already said - this is not supported from Microsoft. But it works very well ;-)