You can fit 285/25/20's, but oversizing the tyre because of the low profile shouldn't be too much of a problem meaning you could also run 30's on the back, but take this into account on your front tyres too.
I have 285/30/21 on 10.5" rims on the back of my S, and I really feel that's the lowest profile you have if you value your wheels!
The S is listed with larger dia rear tyres as an option, but the CLS has the same front and rear. If you went larger on the rear without changing the front dia. it might do strange things to the ESP.