I have read in a number of books dealing with the history of guns, that as guns and gunpowder developed the "experts" came to the (mistaken, as it turned out) conclusion that octagonal barrels were stronger in the breech than round. Please bear in mind, I'm only repeating sources whose own documentation and authority may very well be questionable. Applying the theory to rifles, though, it at least makes sense -- the issue of strength, at the breech in particular, would be more critical with the increase in pressure, rifle vs smoothbore.
I have a small problem with the theory of grinding/filing a barrel octagon, then working it round. Given the tendency of the European nations to wage war on one another and everyone else they came in contact with, it seems that if the first usable stage in a barrel's life was in octagonal form, the need for lots of muskets right NOW would have dictated leaving them octagon, slapping them into stocks, and shipping them out.