After measuring and checking ball sizes in the bore, I find that Uberti 44 bores show daylight up to .46 diameter ball. A .457 ball still shows daylight, so opening up the chambers to that would still have blowby and no longer hold that ball tightly.
Measuring the actual diameter after slugging with a .465 ball was not possible as the bore has 7 grooves, but did show rub marks from the bottom of the grooves.
A .380 ball shows daylight in a 36 bore, Uberti as well.
Though balls like the .465 I have a box of could work with an enlarged chamber, I would hesitate to do all that work, but might try one spare cylinder sometime, as I have a reamer that might work..
Historically, rifling was first invented as an attempt to give fouling a place to go to allow more shots between cleanings. By chance, it was found that accuracy improved, and in an attempt to make the grooves longer, the twist was tried, and accuracy improved even more.
In that light, perhaps the cap & ball bore is oversized for a similar reason, a fouling trap. At some point, there would be no blowby as the grooves fill up with carbon. There is also bullet upset to consider.
Seeing as how my Remington Revolving Rifle (with a 45-70 bore barrel, I built it years ago before Uberti made one) has a 458 bore and can hit a 200 yard 18X24 steel plate consistantly with a 45Colt conversion cylinder in it shooting 452 diameter hard cast bullets, the excess groove depth can't be hurting it too much.
Speaking of Remington, note that the Remington factory Conversion was .46 caliber.