I've seen a lot of custom built revolvers based on the S&W 27/28, 586/686, 29/629 and Ruger GP100 and Redhawks, BlackHawks and Super Blackhawks, all with polygon barrels. This is very common for the long range shooters competing at 200 yards. Shilen and Lothar Walther are common barrel makers in these builds.
The polygon barrels are not impossible to use with lead, but for the best result you need a pretty hard boolit (water quenched WW at least) and the usual mantra about the bullet being sized at least .001-.002" over bore diameter.
I've used this formula with great results in my earlier Desert Eagle, and as we all know they use true polygon barrels. The bullet was the Lee 310gn RF for the .44 Mag.