Ive been using a winamp plugin a whole lot recently called "KB 5.1 Channel v1.00" Coded by someone called Peter Pawlowski.
LINKAGE
It essentialy takes a 2channel mix and upsamples it to 5.1 surround (supports Matrix decoding, Dolby Surround and Dolby Prologic² atm)
Its the best plugin ive ever used bar none for winamp (if a little glitchy at times) and i figure that some developer could code a simmilar setup for VLC to convert 2.0 to 5.1 surround.
Ive got a lot of files that are only 2.0 and they sound alright but it could be better and manualy converting then remuxing the audio is a tiresome effort for a few files and completely demoralising when your looking at converting a few hundred.
The 5.1 support for AC3 already rocks but like i said most of the files i deal with are not AC3 encodes.
Id like to see some 5.1 resampling support placed into VLC (and i know it takes up a lot of resources both in terms of clock cycles and memory generaly resulting in slight audio lag due to buffering) but even something barebones to tinker with would kick some serious ass.