I have the same problem as Vanguardmellophone with my 2005
A6. The sides will start blowing hot air while the center is blowing cold. The problem usually starts on the passenger side first. I also discovered the same remedy - you can reset back to normal AC on all vents when I turn the temp knob up to HI, then to LO, then back to a normal 70 degrees. I also discovered that if I accelarate agressively, sometimes the AC seems to reset too - but this is tough on the engine and not good for gas mileage.
I took the car to my dealer and to a local German car specialist. Both had the car on the computer while the problem was occurring and said there were no error codes. Both claim they never saw the problem becuase it''s a newer model and it would require removing the dashboard to "explore" the situation. Since this involves a lot of work at their hourly $ rate, I have decided to live with the problem.
I joined this Audi Forum to find others with the same problem - not sure what to do next and hope others can offer their consultation.