SoundBlaster do some software which can be used to put stereo CDs out through a choice of speakers. I think it comes with their Audigy range of sound cards. I expect it can be bought seperately too. I think it's called CMSS technology.
If you're on about changing to permanent 5.1 in order to play on your home cinema equipment, then yes and no. Dolby or Sony or whoever own the rights to the encoding on the DVDs for surround sound and it costs an absolute bomb to get a license for it.