I had a relative who was temporarily in the UK pick up a collector's edition for me (because it was unavailable where i live), open the box and e-mail me the cd-key.
Then, instead of waiting for the box to arrive in the mail i installed steam, created an account and pressed "add a game" at the bottom of the window. I entered the key for cliffs of Dover, it appeared in my list of purchased games and started downloading.
The initial order for the game was through Ubi UK so yes, you can buy from anywhere and still download directly from Steam as long as you have a product key to register the sim to your steam account.
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