This is on a nearly brand new 2005 Specialized sirrus elite with tiagra components.
When in the largest 1 or 2 cogs and the middle (sometimes large as well) chainring, the chain will jump off the chainring. If you pedal backwards, the chain will jump down up to 4 cogs and the chain will move off the upper jockey wheel and jam up.
All these symptoms seem to get better if you put too much tension on the front derailleur inner wire, but then the chain rubs on the outer front derailleur cage plate. The rear derailleur is set perfectly and shifts seamlessly in all other gears. It even shifts up to the largest cog perfect.
The front derailleur is set correctly (outer plate parallel to chain, a nickel's width above the large chainring, chain barely rubs inner cage plate when in middle ring/large cog combo.
There is absolutely no wear on the cassette, looks brand new. I can't find any stuck chain links, chain is clean and lubricated.